Polyolefin adhesive compositions for elastic applications

ABSTRACT

The present invention is related to an article comprising a substrate, having at least one propylene terpolymer comprising propylene derived units, one or more dienes, and an alpha-olefin content of less than about 35 wt % of the propylene terpolymer; and an adhesive composition, having about 20 to about 80 wt % of a polymer blend comprising a first propylene-based polymer, that is a homopolymer of propylene or a copolymer of propylene and ethylene or a C 4  to C 10  alpha-olefin, and a second propylene-based polymer, that is a homopolymer of propylene or a copolymer of propylene and ethylene or a C 4  to C 10  alpha-olefin; wherein the second propylene-based polymer is different than the first propylene-based polymer; and wherein the adhesive composition is applied to the substrate at temperature of less than about 150° C.

PRIORITY

This application claims priority to U.S. Application Ser. No. 62/072081filed Oct. 29, 2014, the disclosure of which is fully incorporatedherein by reference.

FIELD OF INVENTION

The invention relates to an article comprising an elastomericcomposition and a polyolefin adhesive composition.

BACKGROUND

Materials with good stretchability and elasticity are used tomanufacture a variety of nonwoven disposable articles in addition todurable articles including incontinence pads, disposable diapers,training pants, clothing, undergarments, sports apparel, automotivetrim, weather-stripping, gaskets, and furniture upholstery. Forclothing, stretchability and elasticity are performance attributes thatallow the materials to provide a closely conforming fit to the body ofthe wearer.

While numerous materials are known to exhibit excellent stress-strainproperties and elasticity at room temperatures, it is often desirablefor elastic materials to provide a conforming or secure fit duringrepeated use, during extensions and retractions at elevated or depressedtemperatures, or in automobile interiors during summer months.Elasticity at elevated temperatures is also important for maintainingtight tolerances throughout temperature cycles. In particular, elasticmaterials used for repeated wear clothing or garments must maintaintheir integrity and elastic performance after laundering.

Spandex, a segmented polyurethane urea elastic material, is currentlyused in various durable fabrics. However, articles made from spandex canlose integrity, shape, and elastic properties when subjected to elevatedtemperatures and polyurethane-based components are costly and do notreadily adhere to olefinic adhesives. U.S. Pat. No. 8,358,291 disclosesa method of making an elastomeric article from a propylene-basedmaterial having good thermal resistance, resistance, stretchability, andelasticity.

To prepare nonwoven articles, hot melt adhesive (HMA) compositions aregenerally used to adhere one or more layers of film and/or fabric. Forsuch articles, HMA compositions are sought that provide a desiredcombination of physical properties such as stable adhesion over timeindicative of broad application temperature ranges, and machinecoatability. Exemplary base polymer compositions and methods of makingpolymer compositions for HMA applications are disclosed in U.S. Pat.Nos. 7,294,681 and 7,524,910. Various polymers described in thesepatents and/or produced by the methods disclosed in these patents havebeen sold by ExxonMobil Chemical Company as LINXAR™ polymers.International Publication No. WO2013/134038 discloses a method forproducing a novel polymer blend having at least two differentpropylene-based polymers produced in parallel reactors. The multi-modalpolymer blend has a Mw of about 10,000 g/mol to about 150,000 g/mol.

Although many different types of polymers are known and have been usedin HMA formulations, such as those using spandex or Lycra®, nonwovenarticles are often prepared using adhesive compositions having highapplication temperatures, around the order of greater than 150° C. Forolefin-based elastomers, the integrity of the elastomeric compositioncan be compromised when adhesives are applied at temperatures above 150°C. Accordingly, there is a need for an adhesive composition that can beapplied at an application temperature of lower than 150° C. to bind oneor more elastomeric articles for manufacturing of a variety of nonwovenapplications.

SUMMARY

The foregoing and/or other challenges are addressed by the methods andproducts disclosed herein.

In one aspect, an article is provided for, where the article comprises(a) a substrate, wherein the substrate comprises at least one propyleneterpolymer comprising propylene derived units, one or more dienes, andone or more C₂ or C₄ to C₂₀ alpha-olefins, where the C₂ or C₄ to C₂₀alpha-olefin content is less than about 35 wt % of the propyleneterpolymer; and (b) an adhesive composition, wherein the adhesivecomposition comprises a polymer blend comprising a first propylene-basedpolymer, wherein the first propylene-based polymer is a homopolymer ofpropylene or a copolymer of propylene and ethylene or a C₄ to C₁₀alpha-olefin, and a second propylene-based polymer, wherein the secondpropylene-based polymer is a homopolymer of propylene or a copolymer ofpropylene and ethylene or a C₄ to C₁₀ alpha-olefin; wherein the secondpropylene-based polymer is different than the first propylene-basedpolymer, and wherein the polymer blend is present in the amount of about20 to about 80 wt % of the adhesive composition; wherein the adhesivecomposition is applied to the substrate at temperature of less thanabout 150° C.

In another aspect, an article is provided, where the article comprises ablend of (a) a composition, wherein the elastomeric compositioncomprises at least one propylene terpolymer comprising propylene derivedunits, one or more dienes, and one or more C₂ or C₄ to C₂₀alpha-olefins, where the C₂ or C₄ to C₂₀ alpha-olefin content is lessthan about 35 wt % of the propylene terpolymer; and (b) an adhesivecomposition, wherein the adhesive composition comprises a polymer blendcomprising a first propylene-based polymer, wherein the firstpropylene-based polymer is a homopolymer of propylene or a copolymer ofpropylene and ethylene or a C₄ to C₁₀ alpha-olefin, and a secondpropylene-based polymer, wherein the second propylene-based polymer is ahomopolymer of propylene or a copolymer of propylene and ethylene or aC₄ to C₁₀ alpha-olefin; wherein the second propylene-based polymer isdifferent than the first propylene-based polymer, and wherein thepolymer blend is present in the amount of about 20 to about 80 wt % ofthe adhesive composition.

In yet another aspect, a method of applying an adhesive composition to asubstrate is provided, where the method comprises the steps of preparinga substrate, wherein the substrate comprises at least one propyleneterpolymer comprising propylene derived units, one or more dienes, andone or more C₂ or C₄ to C₂₀ alpha-olefins, where the C₂ or C₄ to C₂₀alpha-olefin content is less than about 35 wt % of the propyleneterpolymer; and applying an adhesive composition to the substrate at atemperature of less than about 150° C., wherein the adhesive compositioncomprises a polymer blend comprising a first propylene-based polymer,wherein the first propylene-based polymer is a homopolymer of propyleneor a copolymer of propylene and ethylene or a C₄ to C₁₀ alpha-olefin,and a second propylene-based polymer, wherein the second propylene-basedpolymer is a homopolymer of propylene or a copolymer of propylene andethylene or a C₄ to C₁₀ alpha-olefin; wherein the second propylene-basedpolymer is different than the first propylene-based polymer, and whereinthe polymer blend is present in the amount of about 20 to about 80 wt %of the adhesive composition.

These and other aspects of the present inventions are described ingreater detail in the following detailed description and are illustratedin the accompanying figures and tables.

DETAILED DESCRIPTION

The term “polymer” as used herein includes, but is not limited to,homopolymers, copolymers, interpolymers, terpolymers, etc. and alloysand blends thereof. Further, as used herein, the term “copolymer” ismeant to include polymers having two or more monomers, optionally withother monomers, and may refer to interpolymers, terpolymers, etc. Theterm “polymer” as used herein also includes impact, block, graft, randomand alternating copolymers. The term “polymer” shall further include allpossible geometrical configurations unless otherwise specificallystated. Such configurations may include isotactic, syndiotactic andrandom symmetries. “Propylene-based” or “predominantly propylene-based”as used herein, is meant to include any polymer comprising propylene,either alone or in combination with one or more comonomers, in whichpropylene is the major component (i.e., greater than about 50 mol %propylene).

A. Methods of Preparing Adhesive Components and Compositions

A solution polymerization process for preparing a polyolefin adhesivecomponent is generally performed by a system that includes a firstreactor, a second reactor in parallel with the first reactor, aliquid-phase separator, a devolatilizing vessel, and a pelletizer. Thefirst reactor and second reactor may be, for example, continuousstirred-tank reactors.

The first reactor may receive a first monomer feed, a second monomerfeed, and a catalyst feed. The first reactor may also receive feeds of asolvent and an activator. The solvent and/or the activator feed may becombined with any of the first monomer feed, the second monomer feed, orcatalyst feed or the solvent and activator may be supplied to thereactor in separate feed streams. A first polymer is produced in thefirst reactor and is evacuated from the first reactor via a firstproduct stream. The first product stream comprises the first polymer,solvent, and any unreacted monomer.

In any embodiment, the first monomer in the first monomer feed may bepropylene and the second monomer in the second monomer feed may beethylene or a C₄ to C₁₀ olefin. In any embodiment, the second monomermay be ethylene, butene, hexene, and octene. Generally, the choice ofmonomers and relative amounts of chosen monomers employed in the processdepends on the desired properties of the first polymer and final polymerblend. For adhesive compositions, ethylene is a particularly preferredcomonomer for copolymerization with propylene. In any embodiment, therelative amounts of propylene and comonomer supplied to the firstreactor may be designed to produce a polymer that is predominantlypropylene, i.e., a polymer that is more than 50 mol % propylene. Inanother embodiment, the first reactor may produce a homopolymer ofpropylene.

The second reactor may receive a third monomer feed of a third monomer,a fourth monomer feed of a fourth monomer, and a catalyst feed of asecond catalyst. The second reactor may also receive feeds of a solventand activator. The solvent and/or the activator feed may be combinedwith any of the third monomer feed, the fourth monomer feed, or secondcatalyst feed, or the solvent and activator may be supplied to thereactor in separate feed streams. A second polymer is produced in thesecond reactor and is evacuated from the second reactor via a secondproduct stream. The second product stream comprises the second polymer,solvent, and any unreacted monomer.

In any embodiment, the third monomer may be propylene and the fourthmonomer may be ethylene or a C₄ to C₁₀ olefin. In any embodiment, thefourth monomer may be ethylene, butene, hexene, and octene. In anyembodiment, the relative amounts of propylene and comonomer supplied tothe second reactor may be designed to produce a polymer that ispredominantly propylene, i.e., a polymer that is more than 50 mol %propylene. In another embodiment, the second reactor may produce ahomopolymer of propylene.

Preferably, the second polymer is different than the first polymer. Thedifference may be measured, for example, by the comonomer content, heatof fusion, crystallinity, branching index, weight average molecularweight, and/or polydispersity of the two polymers. In any embodiment,the second polymer may comprise a different comonomer than the firstpolymer or one polymer may be a homopolymer of propylene and the otherpolymer may comprise a copolymer of propylene and ethylene or a C₄ toC₁₀ olefin. For example, the first polymer may comprise apropylene-ethylene copolymer and the second polymer may comprise apropylene-hexene copolymer. In any embodiment, the second polymer mayhave a different weight average molecular weight (Mw) than the firstpolymer and/or a different melt viscosity than the first polymer.Furthermore, in any embodiment, the second polymer may have a differentcrystallinity and/or heat of fusion than the first polymer. Specificexamples of the types of polymers that may be combined to produceadvantageous blends are described in greater detail herein.

It should be appreciated that any number of additional reactors may beemployed to produce other polymers that may be integrated with (e.g.,grafted) or blended with the first and second polymers. In anyembodiment, a third reactor may produce a third polymer. The thirdreactor may be in parallel with the first reactor and second reactor orthe third reactor may be in series with one of the first reactor andsecond reactor.

Further description of exemplary methods for polymerizing the polymersdescribed herein may be found in U.S. Pat. No. 6,881,800, which isincorporated by reference herein.

The first product stream and second product stream may be combined toproduce a blend stream. For example, the first product stream and secondproduct stream may supply the first and second polymer to a mixingvessel, such as a mixing tank with an agitator.

The blend stream may be fed to a liquid-phase separation vessel toproduce a polymer rich phase and a polymer lean phase. The polymer leanphase may comprise the solvent and be substantially free of polymer. Atleast a portion of the polymer lean phase may be evacuated from theliquid-phase separation vessel via a solvent recirculation stream. Thesolvent recirculation stream may further include unreacted monomer. Atleast a portion of the polymer rich phase may be evacuated from theliquid-phase separation vessel via a polymer rich stream.

In any embodiment, the liquid-phase separation vessel may operate on theprinciple of Lower Critical Solution Temperature (LCST) phaseseparation. This technique uses the thermodynamic principle of spinodaldecomposition to generate two liquid phases; one substantially free ofpolymer and the other containing the dissolved polymer at a higherconcentration than the single liquid feed to the liquid-phase separationvessel.

Employing a liquid-phase separation vessel that utilizes spinodaldecomposition to achieve the formation of two liquid phases may be aneffective method for separating solvent from multi-modal polymer blends,particularly in cases in which one of the polymers of the blend has aweight average molecular weight less than 100,000 g/mol, and even moreparticularly between 10,000 g/mol and 60,000 g/mol. The concentration ofpolymer in the polymer lean phase may be further reduced by catalystselection. Catalysts of Formula I (described below), particularlydimethylsilyl bis(2-methyl-4-phenylindenyl) zirconium dichloride,dimethylsilyl bis(2-methyl-5-phenylindenyl) hafnium dichloride,dimethylsilyl bis(2-methyl-4-phenylindenyl) zirconium dimethyl, anddimethylsilyl bis(2-methyl-4-phenylindenyl) hafnium dimethyl were foundto be a particularly effective catalysts for minimizing theconcentration of polymer in the lean phase. Accordingly, in anyembodiment, one, both, or all polymers may be produced using a catalystof Formula I, particularly dimethylsilyl bis(2-methyl-4-phenylindenyl)zirconium dichloride, dimethylsilyl bis(2-methyl-4-phenylindenyl)hafnium dichloride, dimethylsilyl bis(2-methyl-4-phenylindenyl)zirconium dimethyl, and dimethylsilyl bis(2-methyl-4-phenylindenyl)hafnium dimethyl.

Upon exiting the liquid-phase separation vessel, the polymer rich streammay then be fed to a devolatilizing vessel for further polymer recovery.In any embodiment, the polymer rich stream may also be fed to a lowpressure separator before being fed to the inlet of the devolatilizingvessel. While in the vessel, the polymer composition may be subjected toa vacuum in the vessel such that at least a portion of the solvent isremoved from the polymer composition and the temperature of the polymercomposition is reduced, thereby forming a second polymer compositioncomprising the multi-modal polymer blend and having a lower solventcontent and a lower temperature than the polymer composition as thepolymer composition is introduced into the vessel. The polymercomposition may then be discharged from the outlet of the vessel via adischarge stream.

The cooled discharge stream may then be fed to a pelletizer where themulti-modal polymer blend is then discharged through a pelletization dieas formed pellets. Pelletization of the polymer may be by an underwater,hot face, strand, water ring, or other similar pelletizer. Preferably anunderwater pelletizer is used, but other equivalent pelletizing unitsknown to those skilled in the art may also be used. General techniquesfor underwater pelletizing are known to those of ordinary skill in theart. International Publication No. WO2013/134038, incorporated herein byreference, generally describes the method of preparing polyolefinadhesive components and compositions.

Polymers for Use in Adhesive Compositions

Preferred polymers are semi-crystalline propylene-based polymers. In anyembodiment, the polymers may have a relatively low molecular weight,preferably about 150,000 g/mol or less. In any embodiment, the polymermay comprise a comonomer selected from the group consisting of ethyleneand linear or branched C₄ to C₂₀ olefins and diolefins. In anyembodiment, the comonomer may be ethylene or a C₄ to C₁₀ olefin.

The term “polymer blend” as used herein includes, but is not limited toa blend of one or more polymers prepared in solution or by physicalblending, such as melt blending.

In any embodiment, one or more polymers of the blend may comprise one ormore propylene-based polymers, which comprise propylene and from about 2mol % to about 30 mol % of one or more comonomers selected from C₂ andC₄-C₁₀ α-olefins. In any embodiment, the α-olefin comonomer units mayderive from ethylene, butene, pentene, hexene, 4-methyl-1-pentene,octene, or decene. The embodiments described below are discussed withreference to ethylene and hexene as the α-olefin comonomer, but theembodiments are equally applicable to other copolymers with otherα-olefin comonomers. In this regard, the copolymers may simply bereferred to as propylene-based polymers with reference to ethylene orhexene as the α-olefin.

In any embodiment, the one or more polymers of the blend may include atleast about 5 mol %, at least about 6 mol %, at least about 7 mol %, orat least about 8 mol %, or at least about 10 mol %, or at least about 12mol % ethylene-derived or hexene-derived units. In those or otherembodiments, the copolymers may include up to about 30 mol %, or up toabout 25 mol %, or up to about 22 mol %, or up to about 20 mol %, or upto about 19 mol %, or up to about 18 mol %, or up to about 17 mol %ethylene-derived or hexene-derived units, where the percentage by moleis based upon the total moles of the propylene-derived and α-olefinderived units. Stated another way, the propylene-based polymer mayinclude at least about 70 mol %, or at least about 75 mol %, or at leastabout 80 mol %, or at least about 81 mol % propylene-derived units, orat least about 82 mol % propylene-derived units, or at least about 83mol % propylene-derived units; and in these or other embodiments, thecopolymers may include up to about 95 mol %, or up to about 94 mol %, orup to about 93 mol %, or up to about 92 mol %, or up to about 90 mol %,or up to about 88 mol % propylene-derived units, where the percentage bymole is based upon the total moles of the propylene-derived andalpha-olefin derived units. In any embodiment, the propylene-basedpolymer may comprise from about 5 mol % to about 25 mol %ethylene-derived or hexene-derived units, or from about 8 mol % to about20 mol % ethylene-derived or hexene-derived units, or from about 12 mol% to about 18 mol % ethylene-derived or hexene-derived units.

The one or more polymers of the blend of one or more embodiments arecharacterized by a melting point (Tm), which can be determined bydifferential scanning calorimetry (DSC). For purposes herein, themaximum of the highest temperature peak is considered to be the meltingpoint of the polymer. A “peak” in this context is defined as a change inthe general slope of the DSC curve (heat flow versus temperature) frompositive to negative, forming a maximum without a shift in the baselinewhere the DSC curve is plotted so that an endothermic reaction would beshown with a positive peak.

In any embodiment, the Tm of the one or more polymers of the blend (asdetermined by DSC) may be less than about 130° C., or less than about120° C., or less than about 115° C., or less than about 110° C., or lessthan about 100° C., or less than about 90° C. In any embodiment, the Tmof the one or more polymers of the blend may be greater than about 25°C., or greater than about 30° C., or greater than about 35° C., orgreater than about 40° C.

In one or more embodiments, the crystallization temperature of thepolymer blend (as determined by DSC) is less than about 110° C., or lessthan about 90° C., or less than about 80° C., or less than about 70° C.,or less than about 60° C., or less than about 50° C., or less than about40° C., or less than about 30° C., or less than about 20° C., or lessthan about 10° C. In the same or other embodiments, the Tc of thepolymer is greater than about 0° C., or greater than about 5° C., orgreater than about 10° C., or greater than about 15° C., or greater thanabout 20° C. In any embodiment, the Tc lower limit of the polymer may be0° C., 5° C., 10° C., 20° C., 30° C., 40° C., 50° C., 60° C., and 70°C.; and the Tc upper limit temperature may be 100° C., 90° C., 80° C.,70° C., 60° C., 50° C., 40° C., 30° C., 25° C., and 20° C. with rangesfrom any lower limit to any upper limit being contemplated.

The polymers suitable for use herein are said to be “semi-crystalline”,meaning that in general they have a relatively low crystallinity. Theterm “crystalline” as used herein broadly characterizes those polymersthat possess a high degree of both inter and intra molecular order, andwhich preferably melt higher than 110° C., more preferably higher than115° C., and most preferably above 130° C. A polymer possessing a highinter and intra molecular order is said to have a “high” level ofcrystallinity, while a polymer possessing a low inter and intramolecular order is said to have a “low” level of crystallinity.Crystallinity of a polymer can be expressed quantitatively, e.g., interms of percent crystallinity, usually with respect to some referenceor benchmark crystallinity. As used herein, crystallinity is measuredwith respect to isotactic polypropylene homopolymer. Preferably, heat offusion is used to determine crystallinity. Thus, for example, assumingthe heat of fusion for a highly crystalline polypropylene homopolymer is190 J/g, a semi-crystalline propylene copolymer having a heat of fusionof 95 J/g will have a crystallinity of 50%. The term “crystallizable” asused herein refers to those polymers which can crystallize uponstretching or annealing. Thus, in certain specific embodiments, thesemi-crystalline polymer may be crystallizable. The semi-crystallinepolymers used in specific embodiments of this invention preferably havea crystallinity of from 2% to 65% of the crystallinity of isotaticpolypropylene. In further embodiments, the semi-crystalline polymers mayhave a crystallinity of from about 3% to about 40%, or from about 4% toabout 30%, or from about 5% to about 25% of the crystallinity ofisotactic polypropylene.

The semi-crystalline polymer can have a level of isotacticity expressedas percentage of isotactic triads (three consecutive propylene units),as measured by ¹³C NMR, of 75 mol % or greater, 80 mol % or greater, 85mol % or greater, 90 mol % or greater, 92 mol % or greater, 95 mol % orgreater, or 97 mol % or greater. In one or more embodiments, the triadtacticity may range from about 75 mol % to about 99 mol %, or from about80 mol % to about 99 mol %, or from about 85 mol % to about 99 mol %, orfrom about 90 mol % to about 99 mol %, or from about 90 mol % to about97 mol %, or from about 80 mol % to about 97 mol %. Triad tacticity isdetermined by the methods described in U.S. Pat. No. 7,232,871.

The semi-crystalline polymer may have a tacticity index m/r ranging froma lower limit of 4, or 6 to an upper limit of 10, or 20, or 25. Thetacticity index, expressed herein as “m/r”, is determined by ¹³C nuclearmagnetic resonance (“NMR”). The tacticity index m/r is calculated asdefined by H. N. Cheng in 17 MACROMOLECULES, 1950 (1984), incorporatedherein by reference. The designation “m” or “r” describes thestereochemistry of pairs of contiguous propylene groups, “m” referringto meso and “r” to racemic. An m/r ratio of 1.0 generally describes anatactic polymer, and as the m/r ratio approaches zero, the polymer isincreasingly more syndiotactic. The polymer is increasingly isotactic asthe m/r ratio increases above 1.0 and approaches infinity.

In one or more embodiments, the semi-crystalline polymer may have adensity of from about 0.85 g/cm³ to about 0.92 g/cm³, or from about 0.86g/cm³ to about 0.90 g/cm³, or from about 0.86 g/cm³ to about 0.89 g/cm³at room temperature and determined according to ASTM D-792. As usedherein, the term “room temperature” is used to refer to the temperaturerange of about 20° C. to about 23.5° C.

In one or more embodiments, the semi-crystalline polymer can have aweight average molecular weight (Mw) of from about 5,000 to about500,000 g/mol, or from about 7,500 to about 300,000 g/mol, or from about10,000 to about 200,000 g/mol, or from about 25,000 to about 175,000g/mol.

Weight-average molecular weight, M_(w), molecular weight distribution(MWD) or M_(w)/M_(n) where M_(n) is the number-average molecular weight,and the branching index, g′(vis), are characterized using a HighTemperature Size Exclusion Chromatograph (SEC), equipped with adifferential refractive index detector (DRI), an online light scatteringdetector (LS), and a viscometer. Experimental details not shown below,including how the detectors are calibrated, are described in: T. Sun, P.Brant, R. R. Chance, and W. W. Graessley, Macromolecules, Volume 34,Number 19, pp. 6812-6820, 2001.

Solvent for the SEC experiment is prepared by dissolving 6 g ofbutylated hydroxy toluene as an antioxidant in 4 L of Aldrich reagentgrade 1,2,4 trichlorobenzene (TCB). The TCB mixture is then filteredthrough a 0.7 μm glass pre-filter and subsequently through a 0.1 μmTeflon filter. The TCB is then degassed with an online degasser beforeentering the SEC. Polymer solutions are prepared by placing the drypolymer in a glass container, adding the desired amount of TCB, thenheating the mixture at 160° C. with continuous agitation for about 2 hr.All quantities are measured gravimetrically. The TCB densities used toexpress the polymer concentration in mass/volume units are 1.463 g/mL atroom temperature and 1.324 g/mL at 135° C. The injection concentrationranges from 1.0 to 2.0 mg/mL, with lower concentrations being used forhigher molecular weight samples. Prior to running each sample the DRIdetector and the injector are purged. Flow rate in the apparatus is thenincreased to 0.5 mL/min, and the DRI was allowed to stabilize for 8-9 hrbefore injecting the first sample. The LS laser is turned on 1 to 1.5 hrbefore running samples.

The concentration, c, at each point in the chromatogram is calculatedfrom the baseline-subtracted DRI signal, I_(DRI), using the followingequation:

c=K _(DRI) I _(DRI)/(dn/dc)

where K_(DRI) is a constant determined by calibrating the DRI, and dn/dcis the same as described below for the LS analysis. Units on parametersthroughout this description of the SEC method are such thatconcentration is expressed in g/cm³, molecular weight is expressed inkg/mol, and intrinsic viscosity is expressed in dL/g.

The light scattering detector used is a Wyatt Technology HighTemperature mini-DAWN. The polymer molecular weight, M, at each point inthe chromatogram is determined by analyzing the LS output using the Zimmmodel for static light scattering (M. B. Huglin, LIGHT SCATTERING FROMPOLYMER SOLUTIONS, Academic Press, 1971):

[K _(O) c/ΔR(θ,c)]=[1/MP(θ)]+2A ₂ c

where ΔR(θ) is the measured excess Rayleigh scattering intensity atscattering angle θ, c is the polymer concentration determined from theDRI analysis, A₂ is the second virial coefficient, P(θ) is the formfactor for a monodisperse random coil (described in the abovereference), and K_(O) is the optical constant for the system:

$K_{o} = \frac{4\pi^{2}{n^{2}\left( {{dn}/{dc}} \right)}^{2}}{\lambda^{4}N_{A}}$

in which N_(A) is the Avogadro's number, and dn/dc is the refractiveindex increment for the system. The refractive index, n=1.500 for TCB at135° C. and λ=690 nm. In addition, A₂=0.0015 and dn/dc=0.104 forethylene polymers, whereas A₂=0.0006 and dn/dc=0.104 for propylenepolymers.

The molecular weight averages are usually defined by considering thediscontinuous nature of the distribution in which the macromoleculesexist in discrete fractions i containing N_(i) molecules of molecularweight M_(i). The weight-average molecular weight, M_(w), is defined asthe sum of the products of the molecular weight M_(i) of each fractionmultiplied by its weight fraction w_(i):

M _(w) =Σw _(i) M _(i)=(ΣN _(i) M _(i) ² /ΣN _(i) M _(i))

since the weight fraction w_(i) is defined as the weight of molecules ofmolecular weight M_(i) divided by the total weight of all the moleculespresent:

w _(i) =N _(i) M _(i) /ΣN _(i) M _(i)

The number-average molecular weight, M_(n), is defined as the sum of theproducts of the molecular weight M_(i) of each fraction multiplied byits mole fraction x_(i):

M _(n) ≡Σx _(i) M _(i) =ΣN _(i) M _(i) /ΣN _(i)

since the mole fraction x_(i) is defined as N_(i) divided by the totalnumber of molecules

x _(i) =N _(i) /ΣN _(i)

In the SEC, a high temperature Viscotek Corporation viscometer is used,which has four capillaries arranged in a Wheatstone bridge configurationwith two pressure transducers. One transducer measures the totalpressure drop across the detector, and the other, positioned between thetwo sides of the bridge, measures a differential pressure. The specificviscosity, η_(s), for the solution flowing through the viscometer iscalculated from their outputs. The intrinsic viscosity, [η], at eachpoint in the chromatogram is calculated from the following equation:

η_(s) =c[η]+0.3(c[η])²

where c was determined from the DRI output.

The branching index (g′, also referred to as g′(vis)) is calculatedusing the output of the SEC-DRI-LS-VIS method as follows. The averageintrinsic viscosity, [η]_(avg), of the sample is calculated by:

$\lbrack\eta\rbrack_{avg} = \frac{\sum{c_{i}\lbrack\eta\rbrack}_{i}}{\sum c_{i}}$

where the summations are over the chromatographic slices, i, between theintegration limits.

The branching index g′ is defined as:

$g^{\prime} = \frac{\lbrack\eta\rbrack_{avg}}{{kM}_{v}^{\alpha}}$

where k=0.000579 and α=0.695 for ethylene polymers; k=0.0002288 andα=0.705 for propylene polymers; and k=0.00018 and α=0.7 for butenepolymers.

M_(v) is the viscosity-average molecular weight based on molecularweights determined by the LS analysis:

M_(v)≡(Σc_(i)M_(i) ^(α)/Σc_(i))^(1/α)

In one or more embodiments, the semi-crystalline polymer may have aviscosity (also referred to a Brookfield viscosity or melt viscosity),measured at 190° C. and determined according to ASTM D-3236 from about100 cP to about 500,000 cP, or from about 100 to about 100,000 cP, orfrom about 100 to about 50,000 cP, or from about 100 to about 25,000 cP,or from about 100 to about 15,000 cP, or from about 100 to about 10,000cP, or from about 100 to about 5,000 cP, or from about 500 to about15,000 cP, or from about 500 to about 10,000 cP, or from about 500 toabout 5,000 cP, or from about 1,000 to about 10,000 cP, wherein 1 cP=1mPa·sec.

In one or more embodiments, the semi-crystalline polymer may becharacterized by its viscosity at 190° C. In one or more embodiments,the semi-crystalline polymer may have a viscosity that is at least about100 cP (centipoise), or at least about 500 cP, or at least about 1,000cP, or at least about 1,500 cP, or at least about 2,000 cP, or at leastabout 3,000 cP, or at least about 4,000 cP, or at least about 5,000 cP.In these or other embodiments, the semi-crystalline polymer may becharacterized by a viscosity at 190° C. of less than about 100,000 cP,or less than about 75,000 cP, or less than about 50,000 cP, or less thanabout 25,000 cP, or less than about 20,000 cP, or less than about 15,000cP, or less than about 10,000 cP, or less than about 5,000 cP withranges from any lower limit to any upper limit being contemplated.

The polymers that may be used in the adhesive compositions disclosedherein generally include any of the polymers according to the processdisclosed in International Publication No. WO2013/134038, incorporatedherein by reference. The triad tacticity and tacticity index of apolymer may be controlled by the catalyst, which influences thestereoregularity of propylene placement, the polymerization temperature,according to which stereoregularity can be reduced by increasing thetemperature, and by the type and amount of a comonomer, which tends toreduce the length of crystalline propylene derived sequences.

Polymers and blended polymer products are also provided. In anyembodiment, one or more of the polymers described herein may be blendedwith another polymer, such as another polymer described herein, toproduce a physical blend of polymers.

Preferably, the polymer blend has a melt flow rate (MFR, 2.16 kg weight@ 230° C.), of greater than about 1,000 g/10 min to less than about10,000 g/10 min as measured according to the ASTM D-1238(A) test methodas modified (described below). Preferably, the MFR of the polymer blendis from greater than about 1,500 g/10 min, or about 2,000 g/10 min, toless than about 3,500 g/10 min, or about 5,000 g/10min, or about 7,500g/10 min.

Preferably, the polymer blend is present in the adhesive composition inthe amount of about 20 wt % to about 80 wt %, preferably about 40 wt %to about 70 wt %, preferably about 50 wt % to about 60 wt % based on theadhesive composition.

Catalysts/Activators to Prepare Adhesive Compositions

The polymers described herein may be prepared using one or more catalystsystems. As used herein, a “catalyst system” comprises at least atransition metal compound, also referred to as catalyst precursor, andan activator. Contacting the transition metal compound (catalystprecursor) and the activator in solution upstream of the polymerizationreactor or in the polymerization reactor of the process described aboveyields the catalytically active component (catalyst) of the catalystsystem. Any given transition metal compound or catalyst precursor canyield a catalytically active component (catalyst) with variousactivators, affording a wide array of catalysts deployable in theprocesses of the present invention. Catalyst systems of the presentinvention comprise at least one transition metal compound and at leastone activator. However, catalyst systems of the current disclosure mayalso comprise more than one transition metal compound in combinationwith one or more activators. Such catalyst systems may optionallyinclude impurity scavengers. Each of these components is described infurther detail below.

The triad tacticity and tacticity index of the polymer may be controlledby the catalyst, which influences the stereoregularity of propyleneplacement, the polymerization temperature, according to whichstereoregularity can be reduced by increasing the temperature, and bythe type and amount of a comonomer, which tends to reduce the length ofcrystalline propylene derived sequences.

In any embodiment, the catalyst systems used for producingsemi-crystalline polymers may comprise a metallocene compound. In anyembodiment, the metallocene compound may be a bridged bisindenylmetallocene having the general formula (In¹)Y(In²)MX₂, where In¹ and In²are identical substituted or unsubstituted indenyl groups bound to M andbridged by Y, Y is a bridging group in which the number of atoms in thedirect chain connecting In¹ with In² is from 1 to 8 and the direct chaincomprises C, Si, or Ge; M is a Group 3, 4, 5, or 6 transition metal; andX₂ are leaving groups. In¹ and In² may be substituted or unsubstituted.If In¹ and In² are substituted by one or more substituents, thesubstituents are selected from the group consisting of a halogen atom,C₁ to C₁₀ alkyl, C₅ to C₁₅ aryl, C₆ to C₂₅ alkylaryl, and Si-, N- orP-containing alkyl or aryl. Each leaving group X may be an alkyl,preferably methyl, or a halide ion, preferably chloride or fluoride.Exemplary metallocene compounds of this type include, but are notlimited to, μ-dimethylsilylbis(indenyl) hafnium dimethyl andμ-dimethylsilylbis(indenyl) zirconium dimethyl.

In any embodiment, the metallocene compound may be a bridged bisindenylmetallocene having the general formula (In¹)Y(In²)MX₂, where In¹ and In²are identical 2,4-substituted indenyl groups bound to M and bridged byY, Y is a bridging group in which the number of atoms in the directchain connecting In¹ with In² is from 1 to 8 and the direct chaincomprises C, Si, or Ge, M is a Group 3, 4, 5, or 6 transition metal, andX₂ are leaving groups. In¹ and In² are substituted in the 2 position bya C₁ to C₁₀ alkyl, preferably a methyl group and in the 4 position by asubstituent selected from the group consisting of C₅ to C₁₅ aryl, C₆ toC₂₅ alkylaryl, and Si-, N- or P-containing alkyl or aryl. Each leavinggroup X may be an alkyl, preferably methyl, or a halide ion, preferablychloride or fluoride. Exemplary metallocene compounds of this typeinclude, but are not limited to,(dimethylsilyl)bis(2-methyl-4-(3,′5′-di-tert-butylphenyl)indenyl)zirconium dimethyl,(dimethylsilyl)bis(2-methyl-4-(3,′5′-di-tert-butylphenyl)indenyl)hafnium dimethyl, (dimethylsilyl)bis(2-methyl-4-naphthylindenyl)zirconium dimethyl, (dimethylsilyl)bis(2-methyl-4-naphthylindenyl)hafnium dimethyl, (dimethylsilyl)bis(2-methyl-4-(N-carbazyl)indenyl)zirconium dimethyl, and(dimethylsilyl)bis(2-methyl-4-(N-carbazyl)indenyl) hafnium dimethyl.

Alternatively, in any embodiment, the metallocene compound maycorrespond to one or more of the formulas disclosed in U.S. Pat. No.7,601,666. Such metallocene compounds include, but are not limited to,dimethylsilylbis(2-(methyl)-5,5,8,8-tetramethyl-5,6,7,8-tetrahydrobenz(f)indenyl)hafnium dimethyl, diphenylsilylbis(2-(methyl)-5,5,8,8-tetramethyl-5,6,7,8-tetrahydrobenz(f)indenyl)hafnium dimethyl, diphenylsilylbis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydrobenz(f)indenyl) hafniumdimethyl, diphenylsilylbis(2-(methyl)-5,5,8,8-tetramethyl-5,6,7,8-tetrahydrobenz(f) indenyl)zirconium dichloride, and cyclo-propylsilylbis(2-(methyl)-5,5,8,8-tetramethyl-5,6,7,8-tetrahydrobenz(f) indenyl)hafnium dimethyl.

In any embodiment, the activators of the catalyst systems used toproduce semi-crystalline polymers may comprise a cationic component. Inany embodiment, the cationic component may have the formula [R¹R²R³AH]⁺,where A is nitrogen, R¹ and R² are together a —(CH₂)_(a)— group, where ais 3, 4, 5, or 6 and form, together with the nitrogen atom, a 4-, 5-,6-, or 7-membered non-aromatic ring to which, via adjacent ring carbonatoms, optionally one or more aromatic or heteroaromatic rings may befused, and R³ is C₁, C₂, C₃, C₄, or C₅ alkyl, or N-methylpyrrolidiniumor N-methylpiperidinium. Alternatively, in any embodiment, the cationiccomponent has the formula [R_(n)AH_(4−n)]⁺, where A is nitrogen, n is 2or 3, and all R are identical and are C₁ to C₃ alkyl groups, such as forexample trimethylammonium, trimethylanilinium, triethylammonium,dimethylanilinium, or dimethylammonium.

A particularly advantageous catalyst that may be employed in anyembodiment is illustrated in Formula I.

In any embodiment, M is a Group IV transition metal atom, preferably aGroup IVB transition metal, more preferably hafnium or zirconium, and Xare each an alkyl, preferably methyl, or a halide ion, preferablychloride or fluoride. Methyl or chloride leaving groups are mostpreferred. In any embodiment, R1 and R2 may be independently selectedfrom the group consisting of hydrogen, phenyl, and naphthyl. R1 ispreferably the same as R2. Particularly advantageous species of FormulaI are dimethylsilyl bis(2-methyl-4-phenylindenyl) zirconium dichloride,dimethylsilyl bis(2-methyl-4-phenylindenyl) zirconium dimethyl,dimethylsilyl bis(2-methyl-4-phenylindenyl) hafnium dichloride, anddimethylsilyl bis(2-methyl-4-phenylindenyl) hafnium dimethyl.

Any catalyst system resulting from any combination of a metallocenecompound, a cationic activator component, and an anionic activatorcomponent mentioned in this disclosure shall be considered to beexplicitly disclosed herein and may be used in accordance with thepresent invention in the polymerization of one or more olefin monomers.Also, combinations of two different activators can be used with the sameor different metallocene(s).

In any embodiment, the activators of the catalyst systems used toproduce the semi-crystalline polymers may comprise an anionic component,[Y]⁻. In any embodiment, the anionic component may be a non-coordinatinganion (NCA), having the formula [B(R⁴)₄]⁻, where R⁴ is an aryl group ora substituted aryl group, of which the one or more substituents areidentical or different and are selected from the group consisting ofalkyl, aryl, a halogen atom, halogenated aryl, and haloalkylaryl groups.The substituents may be perhalogenated aryl groups, or perfluorinatedaryl groups, including, but not limited to, perfluorophenyl,perfluoronaphthyl and perfluorobiphenyl.

Together, the cationic and anionic components of the catalysts systemsdescribed herein form an activator compound. In any embodiment, theactivator may be N,N-dimethylanilinium-tetra(perfluorophenyl)borate,N,N-dimethylanilinium-tetra(perfluoronaphthyl)borate,N,N-dimethylanilinium-tetrakis(perfluorobiphenyl)borate,N,N-dimethylanilinium-tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium-tetra(perfluorophenyl)borate,triphenylcarbenium-tetra(perfluoronaphthyl)borate,triphenylcarbenium-tetrakis(perfluorobiphenyl)borate, ortriphenylcarbenium-tetrakis(3,5-bis(trifluoromethyl)phenyl)borate.

A non-coordinating anion activator may be employed with the catalyst. Aparticularly advantageous activator isdimethylaniliniumtetrakis(heptafluoronaphthyl) borate.

Suitable activators for the processes of the present invention alsoinclude aluminoxanes (or alumoxanes) and aluminum alkyls. Without beingbound by theory, an alumoxane is typically believed to be an oligomericaluminum compound represented by the general formula (R^(x)—Al—O)_(n),which is a cyclic compound, or R^(x) (R^(x)—Al—O)_(n)AlR^(x) ₂, which isa linear compound. Most commonly, alumoxane is believed to be a mixtureof the cyclic and linear compounds. In the general alumoxane formula,R^(x) is independently a C₁-C₂₀ alkyl radical, for example, methyl,ethyl, propyl, butyl, pentyl, isomers thereof, and the like, and n is aninteger from 1-50. In any embodiment, R^(x) may be methyl and n may beat least 4. Methyl alumoxane (MAO), as well as modified MAO containingsome higher alkyl groups to improve solubility, ethyl alumoxane,iso-butyl alumoxane, and the like are useful for the processes disclosedherein.

Further, the catalyst systems suitable for use in the present inventionmay contain, in addition to the transition metal compound and theactivator described above, additional activators (co-activators), and/orscavengers. A co-activator is a compound capable of reacting with thetransition metal complex, such that when used in combination with anactivator, an active catalyst is formed. Co-activators includealumoxanes and aluminum alkyls.

In any embodiment, scavengers may be used to “clean” the reaction of anypoisons that would otherwise react with the catalyst and deactivate it.Typical aluminum or boron alkyl components useful as scavengers arerepresented by the general formula R^(x)JZ₂ where J is aluminum orboron, R^(x) is a C₁-C₂₀ alkyl radical, for example, methyl, ethyl,propyl, butyl, pentyl, and isomers thereof, and each Z is independentlyR^(x) or a different univalent anionic ligand such as halogen (Cl, Br,I), alkoxide (OR^(x)), and the like. Exemplary aluminum alkyls includetriethylaluminum, diethylaluminum chloride, ethylaluminium dichloride,tri-iso-butylaluminum, tri-n-octylaluminum, tri-n-hexylaluminum,trimethylaluminum, and combinations thereof. Exemplary boron alkylsinclude triethylboron. Scavenging compounds may also be alumoxanes andmodified alumoxanes including methylalumoxane and modifiedmethylalumoxane.

Solvents Used to Prepare Adhesive Compositions

The solvent used in the reaction system of the present invention may beany non-polymeric species capable of being removed from the polymercomposition by heating to a temperature below the decompositiontemperature of the polymer and/or reducing the pressure of thesolvent/polymer mixture. In any embodiment, the solvent may be analiphatic or aromatic hydrocarbon fluid.

Examples of suitable, preferably inert, hydrocarbon fluids are readilyvolatile liquid hydrocarbons, which include, for example, hydrocarbonscontaining from 1 to 30, preferably 3 to 20, carbon atoms. Preferredexamples include propane, n-butane, isobutane, mixed butanes, n-pentane,isopentane, neopentane, n-hexane, cyclohexane, isohexane, octane, othersaturated C₆ to C₈ hydrocarbons, toluene, benzene, ethylbenzene,chlorobenzene, xylene, desulphurized light virgin naphtha, and any otherhydrocarbon solvent recognized by those skilled in the art to besuitable for the purposes of this invention. Particularly preferredsolvents for use in the processes disclosed herein are n-hexane andtoluene.

The optimal amount of solvent present in combination with the polymer atthe inlet to the devolatilizer will generally be dependent upon thedesired temperature change of the polymer melt within the devolatilizer,and can be readily determined by persons of skill in the art. Forexample, the polymer composition may comprise, at the inlet of thedevolatilizer, from about 1 wt % to about 50 wt % solvent, or from about5 wt % to about 45 wt % solvent, or from about 10 wt % to about 40 wt %solvent, or from about 10 wt % to about 35 wt % solvent.

International Publication No. WO2013/134038, incorporated herein byreference, generally describes the catalysts, activators, and solventsused to prepare the polymer blend used in the adhesive compositions.

Tackifiers for Use in Adhesive Compositions

The term “tackifier” is used herein to refer to an agent that allows thepolymer of the composition to be more adhesive by improving wettingduring the application. Tackifiers may be produced frompetroleum-derived hydrocarbons and monomers of feedstock including talloil and other polyterpene or resin sources. Tackifying agents are addedto give tack to the adhesive and also to modify viscosity. Tack isrequired in most adhesive formulations to allow for proper joining ofarticles prior to the HMA solidifying.

“Softening Point” is the temperature, measured in ° C., at which amaterial will flow, as determined by ASTM E-28. The one or moretackifiers used in the adhesive composition of the present inventionpreferably have a softening point of about 90° C. to about 120° C.

Although the exemplary formulations disclosed herein focus onformulations in which one or more tackifiers are blended with one ormore polymer blends, adhesive formulations having no tackifier orsubstantially no tackifier are also contemplated. In embodiments, othertackifiers may be used with the polymer blends of the inventionincluding, but not limited to, alkylphenolic, coumarone indene, otherhydrogenated or non-hydrogenated hydrocarbon resins, hydroxylatedpolyester resin, phenolic, pure monomer styrene, resin dispersion, rosinester, rosin, and terpene tackifiers.

Additives: Plasticizer, Wax, Antioxidant for Use in AdhesiveCompositions

The HMA composition can include other additives, e.g., plasticizers,waxes, antioxidants, and combinations thereof either alone or incombination with one or more tackifiers disclosed herein. The HMAcomposition can also include one or more polymer additives, either aloneor in combination with one or more tackifiers, plasticizers, waxes, orantioxidants, and combinations thereof as disclosed herein.

The term “plasticizer” or “oil” is used herein to refer to a substancethat improves the fluidity of a material. Useful commercial availableplasticizers include Primol™ 352, Krystol™ 550, and Nyflex™ 222B.Primol™ 352 is a white oil available from ExxonMobil Chemical. Krystol™550 is a white oil available from Petro-Canada Lubricants. Nyflex™ 222Bis a solvent refined naphthenic oil available from Nynas AB, located inStockholm, Sweden. Preferably, the oil is present in the adhesivecomposition in the amount of up to about 30 wt % of the adhesivecomposition, preferably from about 5 to about 25 wt %, preferably fromabout 10 to about 20 wt %, preferably about 15 to about 25 wt %.

The term “antioxidant” is used herein to refer to high molecular weighthindered phenols and multifunctional phenols. A useful commerciallyavailable antioxidant is Irganox 1010. Irganox 1010 is a hinderedphenolic antioxidant available from BASF SE Corporation located inLudwigshafen, Germany. The invention is not limited to Irganox 1010 asthe antioxidant. In embodiments, other antioxidants that may be usedwith the polymer blends of the invention, including, but are not limitedto amines, hydroquinones, phenolics, phosphites, and thioesterantioxidants.

The term “wax” is used herein to refer to a substance that reduces theoverall viscosity of the adhesive composition. The primary function ofwax is to control the set time and cohesion of the adhesive system.Adhesive compositions of the present invention may comprise paraffin(petroleum) waxes and microcrystalline waxes. In embodiments, theadhesive compositions of the present invention may comprise no wax. Inembodiments, waxes may be used with the polymer blends of the inventionincluding, but not limited to, Castor Oil derivatives (HCO-waxes),ethylene co-terpolymers, Fisher-Tropsch waxes, microcrystalline,paraffin, polyolefin modified, and polyolefin. Preferably, the wax ispresent in the adhesive composition in the amount of up to about 15 wt %of the adhesive composition, preferably from about 5 to about 10 wt %,preferably about 15 wt %.

B. Methods of Preparing Compositions/Substrates

In an embodiment of the present invention, the propylene-α-olefin-dieneterpolymer is an elastomeric composition. As used herein, the term“elastomer” means a polymer that has the ability to be stretched to atleast twice its original length and retract very rapidly toapproximately its original length when released. Such propyleneterpolymers may be combined with optional additives, and the elastomericcomposition may be crosslinked with the addition of a curing agent.

In at least one embodiment, the propylene terpolymer is prepared bypolymerizing propylene with one or more dienes. For example, thepropylene-based polymer can be prepared by polymerizing propylene withethylene and/or at least one C₄-C₂₀ α-olefin, or a combination ofethylene and at least one C₄-C₂₀ α-olefin and one or more dienes. Theone or more dienes can be conjugated or non-conjugated. Preferably, theone or more dienes are non-conjugated.

The alpha olefin comonomers can be linear or branched. Preferred linearcomonomers include ethylene or C₄ to C₈ α-olefins, more preferablyethylene, 1-butene, 1-hexene, and 1-octene, even more preferablyethylene or 1-butene. Preferred branched comonomers include4-methyl-1-pentene, 3-methyl-1-pentene, and 3,5,5-trimethyl-1-hexene. Inone or more embodiments, the comonomer can include styrene.

Illustrative dienes can include but are not limited to5-ethylidene-2-norbornene (ENB); 1,4-hexadiene; 5-methylene-2-norbornene(MNB); 1,6-octadiene; 5-methyl-1,4-hexadiene;3,7-dimethyl-1,6-octadiene; 1,3-cyclopentadiene; 1,4-cyclohexadiene;vinyl norbornene (VNB); dicyclopentadiene (DCPD), and combinationsthereof. Preferably, the diene is ENB.

Preferred methods and catalysts for producing the propylene terpolymersare found in U.S. Pat. Nos. 7,232,871 and 6,881,800 and InternationalPublication No. WO05/049672, which are all incorporated by referenceherein. Pyridine amine complexes, such as those described inInternational Publication No. WO03/040201 are also useful to produce thepropylene terpolymers useful herein. The catalyst can involve afluxional complex, which undergoes periodic intra-molecularre-arrangement so as to provide the desired interruption ofstereoregularity as in U.S. Pat. No. 6,559,262. The catalyst can be astereorigid complex with mixed influence on propylene insertion, seeEP1070087. The catalyst described in EP1614699 could also be used forthe production of backbones suitable for the invention.

The propylene terpolymers can have an average propylene content on aweight percent basis of from about 60 wt % to about 99.7 wt %, morepreferably from about 60 wt % to about 99.5 wt %, more preferably fromabout 60 wt % to about 97 wt %, more preferably from about 65 wt % toabout 95 wt % based on the weight of the polymer. In one embodiment, thebalance comprises one or more dienes and one or more of the α-olefinsdescribed previously. In one or more embodiments above or elsewhereherein, the alpha-olefin is ethylene, butene, hexene, or octene. Inother embodiments, two alpha-olefins are present, preferably ethyleneand one of butene, hexene, or octene.

Preferably, the propylene terpolymer comprises about 0.2 wt % to about24 wt %, of a non-conjugated diene based on the weight of the polymer,more preferably from about 0.5 wt % to about 12 wt %, more preferablyabout 0.6 wt % to about 8 wt %, and more preferably about 0.7 wt % toabout 5 wt %. In one or more embodiments above or elsewhere herein, thepropylene terpolymer comprises ENB in an amount of from about 0.2 toabout 4 wt %, more preferably from about 0.5 to about 2.5 wt %, and morepreferably from about 0.5 to about 2.0 wt %.

In other embodiments, the propylene terpolymer preferably comprisespropylene and diene in one or more of the ranges described above withthe balance comprising one or more of C₂ and/or C₄-C₂₀ olefins. Ingeneral, this will amount to the propylene terpolymer preferablycomprising from about 5 to about 40 wt % of one or more C₂ and/or C₄-C₂₀olefins based the weight of the polymer, preferably less than about 25wt %. Other preferred ranges for the one or more α-olefins include fromabout 5 wt % to about 35 wt %, more preferably from about 5 wt % toabout 30 wt %, more preferably from about 5 wt % to about 25 wt %, morepreferably from about 5 wt % to about 20 wt %, more preferably fromabout 5 to about 17 wt % and more preferably from about 5 wt % to about16 wt %.

The propylene terpolymer can have a weight average molecular weight (Mw)of 5,000,000 or less, a number average molecular weight (Mn) of about3,000,000 or less, a z-average molecular weight (Mz) of about 10,000,000or less, and a g′ index of 0.95 or greater measured at the weightaverage molecular weight (Mw) of the polymer using isotacticpolypropylene as the baseline, all of which can be determined by sizeexclusion chromatography, e.g., 3D SEC, also referred to as GPC-3D asdescribed herein.

In one or more embodiments above or elsewhere herein, the propyleneterpolymer can have a Mw of about 5,000 to about 5,000,000 g/mole, morepreferably a Mw of about 10,000 to about 1,000,000, more preferably a Mwof about 20,000 to about 500,000, more preferably a Mw of about 50,000to about 400,000, wherein Mw is determined as described herein.

In one or more embodiments above or elsewhere herein, the propyleneterpolymer can have a Mn of about 2,500 to about 2,500,000 g/mole, morepreferably a Mn of about 5,000 to about 500,000, more preferably a Mn ofabout 10,000 to about 250,000, more preferably a Mn of about 25,000 toabout 200,000, wherein Mn is determined as described herein.

In one or more embodiments above or elsewhere herein, the propyleneterpolymer can have a Mz of about 10,000 to about 7,000,000 g/mole, morepreferably a Mz of about 50,000 to about 1,000,000, more preferably a Mzof about 80,000 to about 700,000, more preferably a Mz of about 100,000to about 500,000, wherein Mz is determined as described herein.

The molecular weight distribution index (MWD=(Mw/Mn)), sometimesreferred to as a “polydispersity index” (PDI), of the propyleneterpolymer can be about 1.5 to 40. In an embodiment the MWD can have anupper limit of 40, or 20, or 10, or 5, or 4.5, and a lower limit of 1.5,or 1.8, or 2.0. Techniques for determining the molecular weight (Mn andMw) and molecular weight distribution (MWD) can be found in U.S. Pat.No. 4,540,753 (Cozewith, Ju and Verstrate) (which is incorporated byreference herein) and references cited therein, in Macromolecules, 1988,Volume 21, p. 3360 (Verstrate et al.), which is herein incorporated byreference for purposes of, and references cited therein, and inaccordance with the procedures disclosed in U.S. Pat. No. 6,525,157,column 5, lines 1-44, which patent is hereby incorporated by referencein its entirety.

In one or more embodiments above or elsewhere herein, the propyleneterpolymer can have a g′ index value of 0.95 or greater, preferably atleast 0.98, with at least 0.99 being more preferred, wherein g′ ismeasured at the Mw of the polymer using the intrinsic viscosity ofisotactic polypropylene as the baseline. For use herein, the g′ index isdefined as:

$\begin{matrix}{g^{\prime} = \frac{\eta_{b}}{\eta_{l}}} & \;\end{matrix}$

where η_(b) is the intrinsic viscosity of the propylene-based polymerand η_(l) is the intrinsic viscosity of a linear polymer of the sameviscosity-averaged molecular weight (M_(v)) as the propylene-basedpolymer. η_(l)=KM_(v) ^(α), K and α were measured values for linearpolymers and should be obtained on the same instrument as the one usedfor the g′ index measurement.

In one or more embodiments above or elsewhere herein, the propyleneterpolymer can have a density of about 0.85 g/cm³ to about 0.92 g/cm³,more preferably, about 0.87 g/cm³ to 0.90 g/cm³, more preferably about0.88 g/cm³ to about 0.89 g/cm³ at room temperature as measured per theASTM D-1505 test method.

In one or more embodiments above or elsewhere herein, the propyleneterpolymer can have a melt flow rate (MFR, 2.16 kg weight @ 230° C.),equal to or greater than 0.2 g/10 min as measured according to the ASTMD-1238(A) test method as modified (described below). Preferably, the MFR(2.16 kg @ 230° C.) is from about 0.5 g/10 min to about 200 g/10 min andmore preferably from about 1 g/10 min to about 100 g/10 min. In anembodiment, the propylene-based polymer has an MFR of 0.5 g/10 min to200 g/10 min, especially from 2 g/10 min to 30 g/10 min, more preferablyfrom 5 g/10 min to 30 g/10 min, more preferably 10 g/10 min to 30 g/10min, more preferably 10 g/10 min to about 25 g/10 min, or morepreferably 2 g/10 min to about 10 g/10 min.

The propylene terpolymer can have a Mooney viscosity ML (1+4)@125° C.,as determined according to ASTM D1646, of less than 100, more preferablyless than 75, even more preferably less than 60, most preferably lessthan 30.

In one or more embodiments above or elsewhere herein, the propyleneterpolymer can have a heat of fusion (Hf) measured by DifferentialScanning calorimetry (DSC), which is greater than or equal to about 0.5Joules per gram (J/g), and is ≤about 80 J/g, preferably ≤about 75 J/g,preferably ≤about 70 J/g, more preferably ≤about 60 J/g, more preferably≤about 50 J/g, more preferably ≤about 35 J/g. In another embodiment, thepropylene terpolymers can have a heat of fusion (Hf), which is fromabout 0.5 J/g to about 75 J/g, preferably from about 1 J/g to about 75J/g, more preferably from about 0.5 J/g to about 35 J/g. Preferredpropylene terpolymers and compositions can be characterized in terms ofboth their melting points (Tm) and heats of fusion, which properties canbe influenced by the presence of comonomers or steric irregularitiesthat hinder the formation of crystallites by the polymer chains. In oneor more embodiments, the heat of fusion ranges from a lower limit of 1.0J/g, or 1.5 J/g, or 3.0 J/g, or 4.0 J/g, or 6.0 J/g, or 7.0 J/g, to anupper limit of 30 J/g, or 35 J/g, or 40 J/g, or 50 J/g, or 60 J/g or 70J/g, or 75 J/g, or 80 J/g.

The crystallinity of the propylene terpolymer can also be expressed interms of percentage of crystallinity (i.e. % crystallinity). In one ormore embodiments above or elsewhere herein, the propylene terpolymer hasa % crystallinity of from 0.5% to 40%, preferably 1% to 30%, morepreferably 5% to 25% wherein % crystallinity is determined by DSC. Asdisclosed above, the thermal energy for the highest order ofpolypropylene is estimated at 189 J/g (i.e., 100% crystallinity is equalto 209 J/g.).

In addition to this level of crystallinity, the propylene terpolymerpreferably has a single broad melting transition. However, the propyleneterpolymer can show secondary melting peaks adjacent to the principalpeak, but for purposes herein, such secondary melting peaks areconsidered together as a single melting point, with the highest of thesepeaks (relative to baseline as described herein) being considered themelting point of the propylene terpolymer.

The propylene terpolymer preferably has a melting point (measured byDSC) of equal to or less than 100° C., preferably less than 90° C.,preferably less than 80° C., more preferably less than or equal to 75°C., preferably from about 25° C. to about 80° C., preferably about 25°C. to about 75° C., more preferably about 30° C. to about 65° C.

Differential Scanning calorimetry, or DSC, is used to determine heat offusion and melting temperature of the propylene terpolymer. The methodis as follows: about 0.5 grams of polymer is weighed out and pressed toa thickness of about 15-20 mils (about 381-508 microns) at about 140°C-150° C., using a “DSC mold” and Mylar as a backing sheet. The pressedpad is allowed to cool to ambient temperature by hanging in air (theMylar is not removed). The pressed pad is annealed at room temperature(23-25° C.) for about 8 days. At the end of this period, an about 15-20mg disc is removed from the pressed pad using a punch die and is placedin a 10 microliter aluminum sample pan. The sample is placed in aDifferential Scanning calorimeter (Perkin Elmer Pyris 1 Thermal AnalysisSystem) and is cooled to about −100° C. The sample is heated at 10°C./min to attain a final temperature of about 165° C. The thermaloutput, recorded as the area under the melting peak of the sample, is ameasure of the heat of fusion and can be expressed in Joules per gram ofpolymer and is automatically calculated by the Perkin Elmer System. Themelting point is recorded as the temperature of the greatest heatabsorption within the range of melting of the sample relative to abaseline measurement for the increasing heat capacity of the polymer asa function of temperature.

The propylene terpolymer can have a triad tacticity of three propyleneunits, as measured by ¹³C NMR of 75% or greater, 80% or greater, 82% orgreater, 85% or greater, or 90% or greater. Preferred ranges includefrom about 50 to about 99%, more preferably from about 60 to about 99%,more preferably from about 75 to about 99% and more preferably fromabout 80 to about 99%; and in other embodiments from about 60 to about97%. Triad tacticity is determined by the methods described in U.S. Pat.No. 7,232,871.

In one or more embodiments above or elsewhere herein, the propyleneterpolymer can include a blend of two propylene terpolymers differing inthe olefin content, the diene content, or both.

In one or more embodiments above or elsewhere herein, the propyleneterpolymers can include a propylene based elastomeric polymer producedby random polymerization processes leading to polymers having randomlydistributed irregularities in stereoregular propylene propagation. Thisis in contrast to block copolymers in which constituent parts of thesame polymer chains are separately and sequentially polymerized.

In another embodiment, the propylene terpolymers can include copolymersprepared according the procedures in International Publication No.WO02/36651. Likewise, the propylene terpolymers can include polymersconsistent with those described in International Publication Nos.WO03/040201, WO03/040202, WO03/040095, WO03/040233, and/or WO03/040442.Additionally, the propylene terpolymers can include polymers consistentwith those described in EP1233191, and U.S. Pat. No. 6,525,157, alongwith suitable propylene homo- and copolymers described in U.S. Pat. Nos.6,770,713 and 8,198,200, all of which are incorporated by reference. Thepropylene terpolymer can also include one or more polymers consistentwith those described in EP1614699 or EP1017729.

Grafted (Functionalized) Backbone

In one or more embodiments, the propylene terpolymer can be grafted(i.e. “functionalized”) using one or more grafting monomers. As usedherein, the term “grafting” denotes covalent bonding of the graftingmonomer to a polymer chain of the terpolymer. The grafting monomer canbe or include at least one hydrolysable silane component. A preferredhydrolysable silane component can be or include vinyl siloxane.Preferred vinyl siloxanes include vinyl triethoxysilane and vinyltrimethoxysilane.

In one or more embodiments, the grafting monomer can be or include atleast one organic silane having the general formula YSiRR″₂, wherein Yis selected from vinyl terminated radicals, each R″ is independentlyselected from one or more hydrolysable organic radicals; and R can be aY radical, a R″ radical, or selected from C₁ to C₁₀ alkyl radicals (bothR and R″ are bound to the silicon atom). In a particular embodiment, Yis selected from a vinyl radical, vinyl terminated C₁ to C₁₀ alkylradicals, vinyl terminated C₁ to C₁₀ alkoxy radicals, and vinylterminated C₁ to C₁₀ alkoxy radicals. The vinyl terminated radical ispreferably selected from vinyl, allyl, butenyl, cyclohexenyl,cyclopentadienyl, and cyclohexadienyl radicals.

In one or more embodiments, the grafting monomer can be or include oneor more ethylenically unsaturated carboxylic acid or acid derivatives,such as an acid anhydride, ester, salt, amide, imide, acrylates or thelike. Illustrative monomers include but are not limited to: acrylicacid, methacrylic acid, maleic acid, fumaric acid, itaconic acid,citraconic acid, mesaconic acid, maleic anhydride, 4-methylcyclohexene-1,2-dicarboxylic acid anhydride,bicyclo(2.2.2)octene-2,3-dicarboxylic acid anhydride,1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic acid anhydride,2-oxa-1,3-diketospiro(4.4)nonene, bicyclo(2.2.1)heptene-2,3-dicarboxylicacid anhydride, maleopimaric acid, tetrahydrophthalic anhydride,norbornene-2,3-dicarboxylic acid anhydride, nadic anhydride, methylnadic anhydride, himic anhydride, methyl himic anhydride, and5-methylbicyclo(2.2.1)heptene-2,3-dicarboxylic acid anhydride. Othersuitable grafting monomers include methyl acrylate and higher alkylacrylates, methyl methacrylate and higher alkyl methacrylates, acrylicacid, methacrylic acid, hydroxy-methyl methacrylate, hydroxyl-ethylmethacrylate and higher hydroxy-alkyl methacrylates and glycidylmethacrylate. Maleic anhydride is a preferred grafting monomer. The term“maleated polymer” as used herein, refers to a grafted propyleneterpolymer having a maleic copolymer as its grafting monomer.

In one or more embodiments, the grafted propylene terpolymer comprisesof from about 0.5 to about 10 wt % grafting monomer, more preferablyfrom about 0.5 to about 6 wt %, more preferably from about 0.5 to about3 wt %; in other embodiments from about 1 to about 6 wt %, morepreferably from about 1 to about 3 wt %, based on the weight of thepropylene-α-olefin.

Free Radical Initiator

In one or more embodiments, a free radical generating catalyst orinitiator can be used to initiate the graft polymerization reaction.Illustrative initiators include but are not limited to: diacyl peroxidessuch as benzoyl peroxide; peroxyesters such as tert-butylperoxybenzoate, tert-butylperoxy acetate,OO-tert-butyl-O-(2-ethylhexyl)monoperoxy carbonate; peroxyketals such asn-butyl-4,4-di-(tert-butyl peroxy) valerate; and dialkyl peroxides suchas 1,1-bis(tertbutylperoxy) cyclohexane,1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane,2,2-bis(tert-butylperoxy)butane, dicumylperoxide,tert-butylcumylperoxide, di-(2-tert-butylperoxy-isopropyl-(2))benzene,di-tert-butylperoxide (DTBP),2,5-dimethyl-2,5-di(tert-butylperoxy)hexane,2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne, 3,3,5,7,7-pentamethyl1,2,4-trioxepane; and the like. Most preferred free-radical initiatorsare organic peroxides such as benzoyl peroxide, dichlorobenzoylperoxide, dicumyl peroxide, di-tertiary butyl peroxide. The mostpreferred free-radical initiator is dicumyl peroxide. Other suitablefree-radical initiators are described in U.S. Pat. No. 3,646,155.

The free-radical initiator can be added at the same time as the graftingmonomer, or after addition of the grafting monomer. The preferredsequence for the grafting reaction melts the propylene terpolymer, addsand disperses the grafting monomer, introduces the initiator and ventsthe unreacted monomer and by-products resulting from the initiatordecomposition. Other sequences can feed the monomers and the initiatorpre-dissolved in a solvent. Preferably, the free-radical initiator isadded in an amount of from about 0.1 to about 1.0 wt % of thepropylene-α-olefin, more preferably from about 0.05 to about 0.2 wt %.In one or more embodiments, the initiator concentration in the graftedpolymer ranges from about 0.01 wt % to about 4 wt %, from about 0.5 wt %to about 3.8 wt %, from about 1.0 wt % to about 3.3 wt %, or from about0.1 wt % to about 2.0 wt %.

Polyolefinic Thermoplastic Resin

In an embodiment of the present invention, the substrate may contain apolyolefin thermoplastic resin. The term “polyolefinic thermoplasticresin” as used herein refers to any material that is not a “rubber” andthat is a polymer or polymer blend having a melting point of 70° C. ormore and considered by persons skilled in the art as being thermoplasticin nature, e.g., a polymer that softens when exposed to heat and returnsto its original condition when cooled to room temperature. Thepolyolefinic thermoplastic resin can contain one or more polyolefins,including polyolefin homopolymers and polyolefin copolymers. Except asstated otherwise, the term “copolymer” means a polymer derived from twoor more monomers (including terpolymers, tetrapolymers, etc.), and theterm “polymer” refers to any carbon-containing compound having repeatunits from one or more different monomers.

Illustrative polyolefins can be prepared from mono-olefin monomersincluding, but are not limited to, monomers having 2 to 7 carbon atoms,such as ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-hexene,1-octene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene,mixtures thereof and copolymers thereof with (meth)acrylates and/orvinyl acetates. Preferably, the polyolefinic thermoplastic resincomponent is unvulcanized or non crosslinked.

In one or more embodiments, the polyolefinic thermoplastic resincontains polypropylene. The term “polypropylene” as used herein broadlymeans any polymer that is considered a “polypropylene” by personsskilled in the art (as reflected in at least one patent or publication),and includes homo, impact, and random polymers of propylene. Preferably,the polypropylene used in the compositions described herein has amelting point above 110° C., includes at least 90 wt % propylene units,and contains isotactic sequences of those units. The polypropylene canalso include atactic sequences or s syndiotactic sequences, or both. Thepolypropylene can also include essentially syndiotactic sequences suchthat the melting point of the polypropylene is above 110° C. Thepolypropylene can either derive exclusively from propylene monomers(i.e., having only propylene units) or derive from mainly propylene(more than 80% propylene) with the remainder derived from olefins,particularly ethylene, and/or C₄-C₁₀ alpha-olefins. As noted elsewhereherein, certain polypropylenes have a high MFR (e.g., from a low of 10,or 15, or 20 g/10 min to a high of 25 to 30 g/10 min. Others have alower MFR, e.g., “fractional” polypropylenes which have an MFR less than1.0. Those with high MFR can be preferred for ease of processing orcompounding.

In one or more embodiments, the polyolefinic thermoplastic resin is orincludes isotactic polypropylene. Preferably, the polyolefinicthermoplastic resin contains one or more crystalline propylenehomopolymers or copolymers of propylene having a melting temperaturegreater than 105° C. as measured by DSC. Preferred copolymers ofpropylene include, but are not limited to, terpolymers of propylene,impact copolymers of propylene, random polypropylene and mixturesthereof. Preferred comonomers have 2 carbon atoms, or from 4 to 12carbon atoms. Preferably, the comonomer is ethylene. Such polyolefinicthermoplastic resin and methods for making the same are described inU.S. Pat. No. 6,342,565.

The term “random polypropylene” as used herein broadly means a copolymerof propylene having up to 9 wt %, preferably 2 wt % to 8 wt % of analpha olefin comonomer. Preferred alpha olefin comonomers have 2 carbonatoms, or from 4 to 12 carbon atoms. Preferably, the alpha olefincomonomer is ethylene.

In one or more embodiments, the random polypropylene has a 1% secantmodulus of about 100 kPsi to about 200 kPsi, as measured according toASTM D790A. In one or more embodiments, the 1% secant modulus can be 140kPsi to 170 kPsi, as measured according to ASTM D790A. In one or moreembodiments, the 1% secant modulus can be 140 kPsi to 160 kPsi, asmeasured according to ASTM D790A. In one or more embodiments, the 1%secant modulus can range from a low of about 100, 110, or 125 kPsi to ahigh of about 145, 160, or 175 kPsi, as measured according to ASTMD790A.

In one or more embodiments, the random polypropylene can have a densityof about 0.85 to about 0.95 g/cc, as measured by ASTM D792. In one ormore embodiments, the random polypropylene can have a density of about0.89 g/cc to 0.92 g/cc, as measured by ASTM D792. In one or moreembodiments, the density can range from a low of about 0.85, 0.87, or0.89 g/cc to a high of about 0.90, 0.91, 0.92 g/cc, as measured by ASTMD792.

Secondary Elastomeric Component

In an embodiment of the present invention, the substrate may contain oneor more secondary elastomeric components. In at least one specificembodiment, the secondary elastomeric component can be or include one ormore ethylene-propylene copolymers (EP). Preferably, theethylene-propylene polymer (EP) is non-crystalline, e.g., atactic oramorphous, but in certain embodiments the EP may be crystalline(including “semi-crystalline”). The crystallinity of the EP ispreferably derived from the ethylene, and a number of published methods,procedures and techniques are available for evaluating whether thecrystallinity of a particular material is derived from ethylene. Thecrystallinity of the EP can be distinguished from the crystallinity ofthe propylene terpolymer by removing the EP from the composition andthen measuring the crystallinity of the residual propylene terpolymer.Such crystallinity measured is usually calibrated using thecrystallinity of polyethylene and related to the comonomer content. Thepercent crystallinity in such cases is measured as a percentage ofpolyethylene crystallinity and thus the origin of the crystallinity fromethylene is established.

In one or more embodiments, the EP can include one or more optionalpolyenes, including particularly a diene; thus, the EP can be anethylene-propylene-diene (commonly called “EPDM”). The optional polyeneis considered to be any hydrocarbon structure having at least twounsaturated bonds wherein at least one of the unsaturated bonds isreadily incorporated into a polymer. The second bond may partially takepart in polymerization to form long chain branches but preferablyprovides at least some unsaturated bonds suitable for subsequent curingor vulcanization in post polymerization processes. Examples of EP orEPDM copolymers include V722, V3708P, MDV 91-9, V878 that are availableunder the trade name Vistalon from ExxonMobil Chemicals. Severalcommercial EPDM are available from DOW under the trade Nordel IP and MGgrades. Certain rubber components (e.g., EPDMs, such as Vistalon 3666)include additive oil that is preblended before the rubber component iscombined with the thermoplastic. The type of additive oil utilized willbe that customarily used in conjunction with a particular rubbercomponent.

Examples of the optional polyene include, but are not limited to,butadiene, pentadiene, hexadiene (e.g., 1,4-hexadiene), heptadiene(e.g., 1,6-heptadiene), octadiene (e.g., 1,7-octadiene), nonadiene(e.g., 1,8-nonadiene), decadiene (e.g., 1,9-decadiene), undecadiene(e.g., 1,10-undecadiene), dodecadiene (e.g., 1,11-dodecadiene),tridecadiene (e.g., 1,12-tridecadiene), tetradecadiene (e.g.,1,13-tetradecadiene), pentadecadiene, hexadecadiene, heptadecadiene,octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene,tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene,heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, andpolybutadienes having a molecular weight (Mw) of less than 1000 g/mol.Examples of straight chain acyclic dienes include, but are not limitedto 1,4-hexadiene and 1,6-octadiene. Examples of branched chain acyclicdienes include, but are not limited to 5-methyl-1,4-hexadiene,3,7-dimethyl-1,6-octadiene, and 3,7-dimethyl-1,7-octadiene. Examples ofsingle ring alicyclic dienes include, but are not limited to1,4-cyclohexadiene, 1,5-cyclooctadiene, and 1,7-cyclododecadiene.Examples of multi-ring alicyclic fused and bridged ring dienes include,but are not limited to tetrahydroindene; norbornadiene;methyltetrahydroindene; dicyclopentadiene;bicyclo(2.2.1)hepta-2,5-diene; and alkenyl-, alkylidene-, cycloalkenyl-,and cylcoalkyliene norbornenes [including, e.g.,5-methylene-2-norbornene, 5-ethylidene-2-norbornene,5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene,5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, and5-vinyl-2-norbornene]. Examples of cycloalkenyl-substituted alkenesinclude, but are not limited to vinyl cyclohexene, allyl cyclohexene,vinylcyclooctene, 4-vinylcyclohexene, allyl cyclodecene,vinylcyclododecene, and tetracyclododecadiene.

In another embodiment, the secondary elastomeric component can include,but is not limited to, styrene/butadiene rubber (SBR), styrene/isoprenerubber (SIR), styrene/isoprene/butadiene rubber (SIBR),styrene-butadiene-styrene block copolymer (SBS), hydrogenatedstyrene-butadiene-styrene block copolymer (SEBS), hydrogenatedstyrene-butadiene block copolymer (SEB), styrene-isoprene-styrene blockcopolymer (SIS), styrene-isoprene block copolymer (SI), hydrogenatedstyrene-isoprene block copolymer (SEP), hydrogenatedstyrene-isoprene-styrene block copolymer (SEPS),styrene-ethylene/butylene-ethylene block copolymer (SEBE),styrene-ethylene-styrene block copolymer (SES),ethylene-ethylene/butylene block copolymer (EEB),ethylene-ethylene/butylene/styrene block copolymer (hydrogenated BR-SBRblock copolymer), styrene-ethylene/butylene-ethylene block copolymer(SEBE), ethylene-ethylene/butylene-ethylene block copolymer (EEBE),polyisoprene rubber, polybutadiene rubber, isoprene butadiene rubber(IBR), polysulfide, nitrile rubber, propylene oxide polymers,star-branched butyl rubber and halogenated star-branched butyl rubber,brominated butyl rubber, chlorinated butyl rubber, star-branchedpolyisobutylene rubber, star-branched brominated butyl(polyisobutylene/isoprene copolymer) rubber;poly(isobutylene-co-alkylstyrene), preferably isobutylene/methylstyrenecopolymers such as isobutylene/meta-bromomethylstyrene,isobutylene/bromomethylstyrene, isobutylene/chloromethylstyrene,halogenated isobutylene cyclopentadiene, andisobutylene/chloromethylstyrene and mixtures thereof. Preferredsecondary elastomeric components include hydrogenatedstyrene-butadiene-styrene block copolymer (SEBS), and hydrogenatedstyrene-isoprene-styrene block copolymer (SEPS).

The secondary elastomeric component can also be or include naturalrubber. Natural rubbers are described in detail by Subramaniam in RUBBERTECHNOLOGY 179-208 (1995). Suitable natural rubbers can be selected fromthe group consisting of Malaysian rubber such as SMR CV, SMR 5, SMR 10,SMR 20, and SMR 50 and mixtures thereof, wherein the natural rubbershave a Mooney viscosity at 100° C. (ML 1+4) of from 30 to 120, morepreferably from 40 to 65. The Mooney viscosity test referred to hereinis in accordance with ASTM D-1646.

The secondary elastomeric component can also be or include one or moresynthetic rubbers. One suitable commercially available synthetic rubberinclude NATSYN™ (Goodyear Chemical Company), and BUDENE™ 1207 or BR 1207(Goodyear Chemical Company). A desirable rubber is highcis-polybutadiene (cis-BR). By “cis-polybutadiene” or “highcis-polybutadiene”, it is meant that 1,4-cis polybutadiene is used,wherein the amount of cis component is at least 95%. An example of highcis-polybutadiene commercial products used in the composition BUDENE™1207.

The secondary elastomeric component can be present in a range from up toabout 50 phr in one embodiment, from up to about 40 phr in anotherembodiment, and from up to about 30 phr in yet another embodiment. Inone or more embodiments, the amount of the secondary rubber componentcan range from a low of about 1, 7, or 20 phr to a high of about 25, 35,or 50 phr.

Additive Oil

In an embodiment of the present invention, the substrate may contain oneor more additive oils. The term “additive oil” includes both “processoils” and “extender oils”. For example, “additive oil” may includehydrocarbon oils and plasticizers, such as organic esters and syntheticplasticizers. Many additive oils are derived from petroleum fractions,and have particular ASTM designations depending on whether they fallinto the class of paraffinic, naphthenic, or aromatic oils. Other typesof additive oils include mineral oil, alpha olefinic synthetic oils,such as liquid polybutylene, e.g., products sold under the trademarkParapol®. Additive oils other than petroleum based oils can also beused, such as oils derived from coal tar and pine tar, as well assynthetic oils, e.g., polyolefin materials (e.g., SpectaSyn™ andElevast™, both supplied by ExxonMobil Chemical Company.

The ordinarily skilled chemist will recognize which type of oil shouldbe used with a particular rubber, and also be able to determine theamount (quantity) of oil. The additive oil can be present in amountsfrom about 5 to about 300 parts by weight per 100 parts by weight of theblend of the rubber and thermoplastic components. The amount of additiveoil may also be expressed as from about 30 to 250 parts, and moredesirably from about 70 to 200 parts by weight per 100 parts by weightof the rubber component. Alternatively, the quantity of additive oil canbe based on the total rubber content, and defined as the ratio, byweight, of additive oil to total rubber and that amount may in certaincases be the combined amount of process oil and extender oil. The ratiomay range, for example, from about 0 to about 4.0/1. Other ranges,having any of the following lower and upper limits, may also beutilized: a lower limit of 0.1/1, or 0.6/1, or 0.8/1, or 1.0/1, or1.2/1, or 1.5/1, or 1.8/1, or 2.0/1, or 2.5/1; and an upper limit (whichmay be combined with any of the foregoing lower limits) of 4.0/1, or3.8/1, or 3.5/1, or 3.2/1, or 3.0/1, or 2.8/1. Larger amounts ofadditive oil can be used, although the deficit is often reduced physicalstrength of the composition, or oil weeping, or both.

Polybutene oils are preferred. Preferable polybutene oils have an Mn ofless than 15,000, and include homopolymer or copolymer of olefin derivedunits having from 3 to 8 carbon atoms and more preferably from 4 to 6carbon atoms. In one or more embodiments, the polybutene is ahomopolymer or copolymer of a C₄ raffinate. An embodiment of preferredlow molecular weight polymers termed “polybutene” polymers is describedin, for example, SYNTHETIC LUBRICANTS AND HIGH-PERFORMANCE FUNCTIONALFLUIDS 357-392 (Leslie R. Rudnick & Ronald L. Shubkin, ed., MarcelDekker 1999) (hereinafter “polybutene processing oil” or “polybutene”).

In one or more embodiments, the polybutene processing oil is a copolymerhaving at least isobutylene derived units, and optionally 1-butenederived units, and/or 2-butene derived units. In one embodiment, thepolybutene is a homopolymer if isobutylene, or a copolymer ofisobutylene and 1-butene or 2-butene, or a terpolymer of isobutylene and1-butene and 2-butene, wherein the isobutylene derived units are from 40to 100 wt % of the copolymer, the 1-butene derived units are from 0 to40 wt % of the copolymer, and the 2-butene derived units are from 0 to40 wt % of the copolymer. In another embodiment, the polybutene is acopolymer or terpolymer wherein the isobutylene derived units are from40 to 99 wt % of the copolymer, the 1-butene derived units are from 2 to40 wt % of the copolymer, and the 2-butene derived units are from 0 to30 wt % of the copolymer. In yet another embodiment, the polybutene is aterpolymer of the three units, wherein the isobutylene derived units arefrom 40 to 96 wt % of the copolymer, the 1-butene derived units are from2 to 40 wt % of the copolymer, and the 2-butene derived units are from 2to 20 wt % of the copolymer. In yet another embodiment, the polybuteneis a homopolymer or copolymer of isobutylene and 1-butene, wherein theisobutylene derived units are from 65 to 100 wt % of the homopolymer orcopolymer, and the 1-butene derived units are from 0 to 35 wt % of thecopolymer. Commercial examples of a suitable processing oil includes thePARAPOL™ Series of processing oils or Polybutene grades or Indopol™ fromSoltex Synthetic Oils and Lubricants or from BP/Innovene.

The processing oil or oils can be present at about 1 to about 60 phr inone embodiment, and from about 2 to about 40 phr in another embodiment,from about 4 to about 35 phr in another embodiment, and from about 5 toabout 30 phr in yet another embodiment.

Co-Agents

In an embodiment, the substrate may contain one or more co-agents.Suitable co-agents can include liquid and metallic multifunctionalacrylates and methacrylates, functionalized polybutadiene resins,functionalized cyanurate, and allyl isocyanurate. More particularly,suitable co-agents can include, but are not limited to polyfunctionalvinyl or allyl compounds such as, for example, triallyl cyanurate,triallyl isocyanurate, trimethylolpropane trimethacrylate,pentaerthritol tetramethacrylate, ethylene glycol dimethacrylate,diallyl maleate, dipropargyl maleate, dipropargyl monoallyl cyanurate,azobisisobutyronitrile and the like, and combinations thereof.Commercially available co-agents can be purchased from Sartomer.

In one or more embodiments, the substrate contains at least about 0.1 wt% of co-agent based on the total weight of blend. In one or moreembodiments, the amount of co-agent(s) can range from about 0.1 wt % toabout 15 wt %, based on the total weight of blend. In one or moreembodiments, the amount of co-agent(s) can range from a low of about 0.1wt %, 1.5 wt % or 3.0 wt % to a high of about 4.0 wt %, 7.0 wt %, or 15wt %, based on the total weight of blend. In one or more embodiments,the amount of co-agent(s) can range from a low of about 2.0 wt %, 3.0 wt% or 5.0 wt % to a high of about 7.0 wt %, 9.5 wt %, or 12.5 wt %, basedon the total weight of blend. In one or more embodiments, the amount ofco-agent(s) is about 3 wt %, based on the total weight of blend.

Antioxidants

In an embodiment, the substrate may contain one or more anti-oxidants.Suitable anti-oxidants can include hindered phenols, phosphites,hindered amines, Irgafos 168, Irganox 1010, Irganox 3790, Irganox B225,Irganox 1035, Irgafos 126, Irgastab 410, Chimassorb 944, etc. made byCiba Geigy Corp. These may be added to the elastomeric composition toprotect against degradation during shaping or fabrication operationand/or to better control the extent of chain degradation.

In one or more embodiments, the substrate contains at least about 0.1 wt% of antioxidant, based on the total weight of blend. In one or moreembodiments, the amount of antioxidant(s) can range from about 0.1 wt %to about 5 wt %, based on the total weight of blend. In one or moreembodiments, the amount of antioxidant(s) can range from a low of about0.1 wt %, 0.2 wt % or 0.3 wt % to a high of about 1 wt %, 2.5 wt %, or 5wt %, based on the total weight of blend. In one or more embodiments,the amount of antioxidant(s) is about 0.1 wt %, based on the totalweight of blend. In one or more embodiments, the amount ofantioxidant(s) is about 0.2 wt %, based on the total weight of blend. Inone or more embodiments, the amount of antioxidant(s) is about 0.3 wt %,based on the total weight of blend. In one or more embodiments, theamount of antioxidant(s) is about 0.4 wt %, based on the total weight ofblend. In one or more embodiments, the amount of antioxidant(s) is about0.5 wt %, based on the total weight of blend.

Blending and Additives

In one or more embodiments, the individual materials and components,such as the propylene terpolymer, grafting monomer, free radicalinitiator, and optionally the one or more polyolefinic thermoplasticresins, secondary elastomeric component, additive oil, co-agents, andanti-oxidants can be blended by melt-mixing to form a blend. Examples ofmachinery capable of generating the shear and mixing include extruderswith kneaders or mixing elements with one or more mixing tips orflights, extruders with one or more screws, extruders of co or counterrotating type, Banbury mixer, Farrell Continuous mixer, and the BussKneader. The type and intensity of mixing, temperature, and residencetime required can be achieved by the choice of one of the above machinesin combination with the selection of kneading or mixing elements, screwdesign, and screw speed (<3000 RPM).

In one or more embodiments, the blend can include the propyleneterpolymer in an amount ranging from a low of about 51 wt %, 60 wt %, 70wt %, or 75 wt % to a high of about 80 wt %, 90 wt %, 95 wt %, or 99 wt%. In one or more embodiments, the blend can include the one or morepolyolefinic thermoplastic components in an amount ranging from a low ofabout 5 wt %, 10 wt %, or 20 wt % to a high of about 25 wt %, 30 wt %,or 40 wt %. In one or more embodiments, the blend can include thesecondary elastomeric component in an amount ranging from a low of about5 wt %, 10 wt %, or 15 wt % to a high of about 20 wt %, 35 wt %, or 40wt %. In one or more embodiments, the blend can include the one or moreadditives, co-agents, and/or anti-oxidants in an amount ranging from alow of about 0.001 wt %, 0.01 wt %, or 0.1 wt % to a high of about 0.5wt %, 1.0 wt %, 2.5 wt %, or 5.0 wt %. Unless otherwise noted herein,all weight percents (wt %) are based on the total weight of the blendedcomposition.

In one or more embodiments, the co-agents, antioxidants, and/or otheradditives can be introduced at the same time as the other polymercomponents or later downstream in case of using an extruder or Busskneader or only later in time. In addition to the co-agents andantioxidants described, other additives can include antiblocking agents,antistatic agents, ultraviolet stabilizers, foaming agents, andprocessing aids. The additives can be added to the blend in pure form orin master batches.

Conventional propylene terpolymers are disclosed, for example, in U.S.Pat. Nos. 6,525,157, 6,500,563, and 6,342,565, each of which is hereinincorporated by reference in its entirety. U.S. Pat. No. 6,342,565, inparticular, discloses a soft, set-resistant, annealed fiber comprising ablend of polyolefins. Other conventional compositions are described inInternational Publication Nos. WO04/014988, WO03/040233, WO00/69963,EP946640, EP964641, EP969043, and EP1098934, each of which is hereinincorporated by reference in its entirety. EP1003814 and U.S. Pat. No.6,642,316, each of which is herein incorporated by reference in itsentirety, disclose two-component blends of small amounts of isotacticpolypropylene and an ethylene based elastomer. EP374695 discloses twocomponent blends using 40 wt % or less of the propylene-based copolymer.EP0510559, International Publication No. WO2005/003199, U.S. Pat. Nos.6,472,015, 6,455,637, 5,844,009, 5,883,145, U.S. Patent Publication2002/0151647 and U.S. Pat. No. 6,794,453, each of which is hereinincorporated by reference in its entirety, disclose graftedpolyethylene-based compositions having at least 50 wt % ethylene derivedunits.

One problem with using polyethylene-based polymers in forming graftpolymers is that the peroxides that are used to initiate the graftingalso act as a cross-linking agent towards polyethylene. Thus, whatresults from contacting peroxides with polyethylene-based polymers is ahighly cross-linked polymer with higher molecular weight, and highviscosity, which is even worse when high silane levels, whichnecessitate the use of high levels of peroxides, are required to gethigher performance. Such compositions are not suitable for stretchableapplication as they lack stretchability at room and elevatedtemperatures due to its crystalline nature.

The article S. Yang et al., “Mechanism of a One-Step Method forPreparing Silane Grafting and Cross-linking Polypropylene” in 47 POLYMERENGINEERING AND SCIENCE, 1004 (2007), which is incorporated herein byreference, discloses the grafting of silane to polypropylene, thusforming moisture cross-linkable propylene homopolymer. Other relatedreferences include U.S. Pat. Nos. 3,646,155, 7,464,696, 8,013,093,7,928,165, and 7,605,217, each of which is incorporated herein byreference.

Preparing Grafted Propylene Terpolymers

In an embodiment, a grafted propylene terpolymer can be used to preparethe article. The grafted propylene terpolymer can be prepared usingconventional techniques, for example, the graft polymer can be preparedin solution, in a fluidized bed reactor, or by melt grafting. Apreferred grafted polymer can be prepared by melt blending in ashear-imparting reactor, such as an extruder reactor. Single screw butpreferably twin screw extruder reactors such as co-rotating intermeshingextruder or counter-rotating non-intermeshing extruders but alsoco-kneaders such as those sold by Buss are especially preferred.

In at least one specific embodiment, the propylene terpolymer, graftingmonomer, free-radical initiator, and optionally one or more polyolefinicthermoplastic resins, and optionally one or more elastomers can bereacted at a temperature above the melting point of the propyleneterpolymer under conditions at which the propylene-based polymer issubjected to mechanical shearing, using processes known to those skilledin the art. The grafted propylene terpolymer can be subsequentlymelt-processed (such as by a Brabender or single or double screwextruder that can apply a shearing force on the molten material), in oneembodiment with an amount of one or more condensation catalysts thatfacilitate the cross-linking reaction of the grafted copolymer afterfabricating into articles of use. The condensation catalyst (or“catalyst”) can be selected from the group consisting of organic bases,carboxylic acids and organometallic compounds including organictitanates and complexes or carboxylates of lead, cobalt, iron, nickel,zinc and tin. Preferably, the catalyst is selected from dibutyltindilaurate, dibutyltin diacetate, dibutyltin octanoate, dioctyltinmaleate, dibutyltin oxide and titanium compounds such astitanium-2-ethylhexoxide. A preferred condensation catalyst includesdibutyl tindilaurate, though any material that will catalyze thecondensation reaction is suitable. The condensation catalyst ispreferably added in an amount of from 0.01 to 5 wt %, and from 0.01 to 3wt % in another embodiment, more preferably 0.05 to 2 wt %, and mostpreferably 0.1 to 1 wt % (by weight of the grafted propyleneterpolymer). In one or more embodiments, the amount of condensationcatalyst ranges from about 0.01 wt % to about 5 wt %, from about 0.5 wt% to about 4.2 wt %, from about 1.0 wt % to about 3.3 wt %, or fromabout 0.1 wt % to about 2.0 wt %, based on total weight of the blendcomposition.

Subjecting the composition thus produced to moisture, at an elevatedtemperature of greater than about 20° C., or greater than about 30° C.,or greater than about 40° C. or greater than about 50° C., preferably offrom 20° C. to 85° C., will induce crosslinking of the silane groups viaa combined hydrolysis and condensation reaction. Atmospheric moisture isusually sufficient to permit the crosslinking to occur, but the rate ofcrosslinking may be increased by the use of an artificially moistenedatmosphere, or by immersion in liquid water. For example, crosslinkingis induced by a relative humidity of at least about 50%, or at leastabout 60%, or at least about 75% for at least about 10 hours, or atleast about 25 hours, or at least about 50 hours, or at least about 75hours. Preferably crosslinking is induced by exposure to at least about90% relative humidity for approximately 100 hours. Also, subjecting thecomposition to heat and moisture will accelerate the crosslinkingreaction. Most preferably, crosslinking is effected at a temperature ofat least about 50° C. and most preferably by exposing the composition toa temperature of about 85° C. and a relative humidity of about 90% forapproximately 100 hours. The end result is a cross-linked propyleneterpolymer (or “cross-linked copolymer blend”).

In at least one other specific embodiment, the propylene terpolymer,grafting monomer, free-radical initiator, and condensation catalyst, andoptional polyolefinic thermoplastic resins, elastomers, and/oradditives, can be pre-blended and passed through an extruder at atemperature above the melting point of the propylene-based polymer anddecomposition temperature of the peroxide, in order to graft the silaneonto the propylene-based polymer. Thus is produced the grafted propyleneterpolymer (or copolymer blend composition). The grafted polymer canthen be passed through a multi-strand die, cooled, and subsequentlychopped into pellets with a strand pelletizer and dried. The pellets canthen be melted and fabricated into a formed article that can be exposedto moisture at any time, preferably at a temperature above about 50° C.and most preferably by exposing the composition to a temperature ofabout 85° C. and a relative humidity of about 90% for approximately 100hours, to effect crosslinking of the material.

Cured Products

Formed articles include extruded articles, such as pellets, fabric, orfilms, and articles made therefrom, such as coatings, nonwoven fabrics,and woven fabrics. Preferably the articles are at least partiallycrosslinked or cured. Preferably, the formed article is at leastpartially crosslinked or cured so that the article becomesheat-resistant. As used herein, the term “heat-resistant” refers to theability of a polymer composition or an article formed from a polymercomposition to pass the high temperature heat-setting and dyeing testsdescribed herein. As used herein, the terms “cured”, “crosslinked”, “atleast partially cured”, and “at least partially crosslinked” refer to acomposition having at least 2 wt % insolubles based on the total weightof the composition. In one or more embodiments, the compositionsdescribed herein can be cured to a degree so as to provide at least 3 wt%, or at least 5 wt %, or at least 10 wt %, or at least 20 wt %, or atleast 35 wt %, or at least 45 wt %, or at least 65 wt %, or at least 75wt %, or at least 85 wt %, or less than 95 wt % insolubles using Xyleneas the solvent by Soxhlet extraction. It is appreciated that any meansof crosslinking known in the art can be used in the present invention,including electronic beam, ultra-violet radiation, gamma radiation,moisture curing, and/or chemical cross-linking.

In a particular embodiment, the crosslinking is accomplished by exposingthe grafted elastomeric composition to water (“moisture cure”). Thegrafted, elastomeric composition can be moisture cured after shaping orextruding the article or before shaping or extruding the article.

C. Applications of Articles Comprising Elastomeric Compositions andAdhesives

The adhesive formulations disclosed herein can be used in variousnonwoven construction applications including, but not limited to,hygiene products such as baby diapers, adult diapers, incontinenceproducts or devices, absorbent articles, panty liners, and sanitarynapkins. The adhesive formulations disclosed herein can also be used invarious nonwoven elastic applications including, but not limited to,hygiene products such as wound care dressings for human or veterinarymedicine. As the hygiene industry is continuing to move to products,articles, and devices with thinner gauge films and thinner nonwovenmaterials, the industry is continuing to seek adhesive formulations thatcan be applied over a broad application temperature range, forversatility of an adhesive formulation in more than one end use product,article, device, and combinations thereof. The adhesive formulationsdescribed herein, having a high polymer load, provide a desiredcombination of physical properties such as stable adhesion over timeindicative of broad application temperature ranges and machinecoatability and therefore can be used in nonwoven applications includinghygiene products disclosed herein. It should be appreciated that theadhesive formulations of the present disclosure, while being well suitedfor use in hygiene nonwoven products, may also find utility in otherapplications as well.

In embodiments, one or more adhesive formulations can be used in baby oradult diapers, incontinence product, or training pants. One or moreadhesive formulations disclosed herein may be used alone or incombination with other additives for affixing and or securing differentlayers or different components of a disposable diaper, incontinenceproduct, or training pant construction. The construction of a diaper,incontinence product, or training pant can be accomplished in anyconventional manner known in the art.

In a common construction, a diaper, incontinence product, or trainingpant includes a pant body having a front section, a back section, acrotch section, two elastic sections each having a front elastic memberand a back elastic member, two leg openings and a waist opening, abacksheet and a topsheet, a waistband and two leg bands, a waistborderand two leg borders, an absorbent article, and optionally a fasteningdevice having a quick-remove peelable layer on the fastening device whenthe diaper, incontinence product, or training pant is not in use.Certain non-limiting examples of using one or more adhesive formulationsof the present disclosure in a diaper, incontinence product, or trainingpant include attaching the sides of the front section to the backsection, attaching the crotch section to the front section and the backsection, attaching the topsheet to the front layer, attaching thebacksheet to the back layer, attaching the absorbent article to thecrotch section, attaching each of the leg bands to each of the legopenings of the topsheet and backsheet, attaching each of the legborders to each of the leg bands, attaching the waistband to the topsection of the top sheet and the top section of the backsheet, attachingthe waistborder to the waistband, attaching the quick-remove peelablelayer to the fastening device, and attaching the fastening device to thewaistborder.

In embodiments, one or more adhesive formulations can be used insanitary napkins or panty liners. As used herein, the term “sanitarynapkin” refers to an externally positioned, disposable absorbent articlein the form of a catamenial device, configured for the absorption ofbody fluids such as menses. As used herein, the term “panty liner”refers to an externally positioned, disposable absorbent article havinga thinner gauge and a narrower width than a sanitary napkin that can beconfigured for the absorption of body fluids. The construction of asanitary napkin or panty liner can be accomplished in any conventionalmanner known in the art.

In a common construction, a sanitary napkin or panty liner includes afront body having an absorbent article, back body to be positioned onthe undergarment of the wearer, a quick-remove peelable protectablelayer covering the back body when the sanitary napkin or panty liner isnot in use, optionally two side wing projections on either side of thefront body and a quick-remove peelable protective layer covering each ofthe two side wing projections when the sanitary napkin or panty liner isnot in use. Certain non-limiting examples of using one or more adhesiveformulations of the present disclosure in a sanitary napkin or pantyliner include attaching an absorbent article to the front body,attaching the front body to the back body, attaching a quick-removepeelable protective layer to the back body, attaching the two side wingprojections on the front body, and attaching a quick-remove peelableprotective layer to each of the two side wing projections on the frontbody.

In embodiments, one or more adhesive formulations can be used in a woundcare dressing for human or veterinary medicine. As used herein, the term“wound care dressing” refers to wet, dry, or a combination of wet anddry, gauze used at or around a wound site to help wound healing. Theconstruction of a wound care dressing can be accomplished in anyconventional manner known in the art. In a common construction, a woundcare dressing includes a top layer that is visible to the patient and abottom layer that is in contact with the wound, an absorbent article, anadhesive coating the bottom layer, and a quick-remove peelableprotective layer covering the bottom layer when the wound care dressingis not in use. Certain non-limiting examples of using one or moreadhesive formulations of the present disclosure in a wound care dressinginclude attaching an absorbent article to the bottom layer, attachingthe bottom layer to the top layer, attaching the quick-remove peelableprotective layer to the bottom layer, and attaching the adhesive coatingto the bottom layer.

In an embodiment of the present invention, the adhesive composition andthe elastomeric composition are blended to form an article. The adhesivecomposition in such an article may be present in the amount of less thanabout 20 wt %, preferably about 5 wt % to about 20 wt %, or 10 wt % toabout 20 wt %, or about 15 wt % to about 20 wt %.

EXAMPLES

In a pilot plant, propylene-ethylene copolymers were produced byreacting a feed stream of propylene with a feed stream of ethylene inthe presence of a metallocene catalyst to produce a polymer blend inaccordance with the method disclosed herein and in InternationalPublication No. WO2013/134038. The polymer blend PB1 of the example ofthe invention has an ethylene content of about 11.5 wt %, a meltviscosity at 190° C. of about 7175 cP, a Melt Flow Rate (MFR) (230° C.,2.16 kg) of about 2,000 g/10 min, a Heat of Fusion of about 25 J/g, aShore Hardness C of about 25, a Melting Temperature of about 104° C.,and a Crystallization Temperature of about 42° C. The polymer blend PB2of the example of the invention has an ethylene content of about 12.4 wt%, a melt viscosity at 190° C. of about 4110 cP, a Melt Flow Rate (MFR)(230° C., 2.16 kg) of about 3,500 g/10 min, a Heat of Fusion of about 23J/g, a Shore Hardness C of about 29, a Melting Temperature of about 95°C., and a Crystallization Temperature of about 27° C. The invention isnot limited to PB1 or PB2 as the polymer blend.

To prepare the propylene terpolymers of the present invention, twodifferent streams, each with a ratio of propylene, ENB, and ethylene wasfed into two reactors in accordance with the method disclosed herein.The propylene terpolymers of the present invention are listed inTable 1. The invention is not limited to the terpolymers of Table 1. Allof the terpolymers of Table 1 were then compounded with 3 wt % SR 350 (acrosslinking enhancer/co-agent), Irgafos 168 (an antioxidant), and 5 wt% PP 5341 (a polypropylene homopolymer). Injection molding techniquesknown in the art were then used to prepare plaques of the terpolymer andcompounded additives. The injection molded plaques were then crosslinkedby e-beam irradiation (45 kGy and 60 kGy from Ebeam Services).

TABLE 1 Propylene Ethylene Melt Flow Rate, Diene Terpolymer Content, %g/10 min Content, % PT1 13.5 4.3 2.4 PT2 14.2 4.2 1.6 PT3 14.5 8.2 2.5PT4 17.0 7.4 1.8

To prepare the adhesive composition of the present invention, variousamounts of tackifiers and other additives were blended with one of thepolymer blends described above (PB1 or PB2). The adhesive compositionsof the present invention are listed in Table 2. The invention is notlimited to the adhesives in Table 2.

TABLE 2 Adhesive Viscosity, Polymer Blend Tackifier Other Additives 140°C. (wt %) (wt %) (wt %) (cP) 50% PB1 40% Escorez ™ 10% Krystol 550 6,6005400 45% PB1 40% Escorez ™ 0.2% Irganox1010/ 7,600 5380 10% Krystol 550/5% Kraton FG 1901 40% PB1 40% Escorez ™ 0.2% Irganox1010/ 5380 10%Krystol 550/ 5% Kraton FG 1901/ 5% Polywax 2000 70% PB2 20% Escorez ™0.2% Irganox1010/ 7,600 5400 10% Polywax 2000 65% PB2 20% Escorez ™ 0.2%Irganox1010/ 5400 5% Krystol 550/ 10% Polywax 2000

The application temperature was set to 140° C., the speed was fixed at75 feet/minute and the add-on to 6 g/m². “Application Temperature” isthe temperature, in ° C., at which an adhesive formulation is applied tobond two substrates together, where the substrates can be the same ordifferent. Each adhesive of Table 2 was separately tested on each of thecrosslinked injection molded plaques.

To evaluate the adhesive properties of the resultant article, theadhesive-covered plaques were aged for 24 hours at room temperature andpulled at 180° direction to evaluate the adhesion strength. As usedherein, the term “room temperature” is used to refer to the temperaturerange of about 20° C. to about 23.5° C. For all samples, the adhesivecomposition indicated strong adhesive strength to the polymer plaque.Accordingly, the adhesive formulations of the present invention can beused in construction/laminated nonwovens and for elastic nonwovensalike, preferably for nonwoven construction articles, products, anddevices. The formulations may also find utility in other aspects ofnonwoven construction.

Certain embodiments and features have been described using a set ofnumerical upper limits and a set of numerical lower limits. It should beappreciated that ranges from any lower limit to any upper limit arecontemplated unless otherwise indicated. Certain lower limits, upperlimits, and ranges appear in one or more claims below. All numericalvalues are “about” or “approximately” the indicated value, and take intoaccount experimental error and variations that would be expected by aperson having ordinary skill in the art.

To the extent a term used in a claim is not defined above, it should begiven the broadest definition persons in the pertinent art have giventhat term as reflected in at least one printed publication or issuedpatent. Furthermore, all patents, test procedures, and other documentscited in this application are fully incorporated by reference to theextent such disclosure is not inconsistent with this application and forall jurisdictions in which such incorporation is permitted.

We claim:
 1. An article comprising (a) a substrate, comprising at leastone propylene terpolymer comprising propylene derived units, one or moredienes, and one or more C₂ or C₄ to C₂₀ alpha-olefins, where the C₂ orC₄ to C₂₀ alpha-olefin content is less than about 35 wt % of thepropylene terpolymer; and (b) an adhesive composition, comprising apolymer blend comprising a first propylene-based polymer, wherein thefirst propylene-based polymer is a homopolymer of propylene or acopolymer of propylene and ethylene or a C₄ to C₁₀ alpha-olefin, and asecond propylene-based polymer, wherein the second propylene-basedpolymer is a homopolymer of propylene or a copolymer of propylene andethylene or a C₄ to C₁₀ alpha-olefin; wherein the second propylene-basedpolymer is different than the first propylene-based polymer, and whereinthe polymer blend is present in the amount of about 20 to about 80 wt %of the adhesive composition; wherein the adhesive composition is appliedto the substrate at temperature of less than about 150° C.
 2. Thearticle of claim 1, wherein the substrate further comprises one or moresecondary elastomeric components, one or more polyolefinic thermoplasticresins, or at least one of each. 3.-15. (canceled)
 16. A method ofapplying an adhesive composition to a substrate, wherein the methodcomprises the steps of : (a) preparing a substrate, comprising at leastone propylene terpolymer comprising propylene derived units, one or moredienes, and one or more C₂ or C₄ to C₂₀ alpha-olefins, where the C₂ orC₄ to C₂₀ alpha-olefin content is less than about 35 wt % of thepropylene terpolymer; and (b) applying an adhesive composition to thesubstrate at a temperature of less than about 150° C., wherein theadhesive composition comprises a polymer blend comprising a firstpropylene-based polymer, wherein the first propylene-based polymer is ahomopolymer of propylene or a copolymer of propylene and ethylene or aC₄ to C₁₀ alpha-olefin, and a second propylene-based polymer, whereinthe second propylene-based polymer is a homopolymer of propylene or acopolymer of propylene and ethylene or a C₄ to C₁₀ alpha-olefin; whereinthe second propylene-based polymer is different than the firstpropylene-based polymer, and wherein the polymer blend is present in theamount of about 20 to about 80 wt % of the adhesive composition.
 17. Themethod of claim 16, wherein the polymer blend has a melt flow rate ofgreater than about 1,000 g/10 min to less than about 10,000 g/10 min.18. The method of claim 16, wherein the propylene terpolymer of thesubstrate comprises of from about 0.2 to about 4 wt %5-ethylidene-2-norbornene (ENB) based on the propylene terpolymer. 19.The method of claim 16, wherein the substrate is a film or fabric. 20.An article produced by the method according to claim 16.